[go: up one dir, main page]

WO2018003142A1 - Composition pour formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de fabrication de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire - Google Patents

Composition pour formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de fabrication de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire Download PDF

Info

Publication number
WO2018003142A1
WO2018003142A1 PCT/JP2016/086388 JP2016086388W WO2018003142A1 WO 2018003142 A1 WO2018003142 A1 WO 2018003142A1 JP 2016086388 W JP2016086388 W JP 2016086388W WO 2018003142 A1 WO2018003142 A1 WO 2018003142A1
Authority
WO
WIPO (PCT)
Prior art keywords
passivation layer
composition
forming
group
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/086388
Other languages
English (en)
Japanese (ja)
Inventor
剛 早坂
野尻　剛
田中　直敬
光祥 濱田
麻理 清水
児玉　俊輔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of WO2018003142A1 publication Critical patent/WO2018003142A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a composition for forming a passivation layer, a semiconductor substrate with a passivation layer, a method for manufacturing a semiconductor substrate with a passivation layer, a solar cell element, a method for manufacturing a solar cell element, and a solar cell.
  • a p-type silicon substrate having a textured structure is prepared so as to promote the light confinement effect and achieve high efficiency, and subsequently, in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen and oxygen, 800 ° C. to 900 ° C. Several tens of minutes are performed at a temperature to uniformly form the n-type diffusion layer on the surface of the p-type silicon substrate.
  • phosphorus oxychloride POCl 3
  • nitrogen and oxygen 800 ° C. to 900 ° C.
  • n-type diffusion layers are formed not only on the light-receiving surface of the p-type silicon substrate but also on the side surface and the back surface. Therefore, side etching is performed to remove the n-type diffusion layer formed on the side surface. Further, the n-type diffusion layer formed on the back surface needs to be converted into a p + -type diffusion layer. For this reason, the n-type diffusion layer is converted into a p + -type diffusion layer by applying an aluminum paste containing aluminum powder and a binder to the whole or a part of the back surface and heat-treating (baking) the aluminum paste, and an aluminum electrode The ohmic contact is obtained by forming.
  • the aluminum electrode formed from the aluminum paste has low conductivity. Therefore, in order to reduce the sheet resistance of the aluminum electrode, the aluminum electrode generally formed on the entire back surface must have a thickness of about 10 ⁇ m to 20 ⁇ m after heat treatment (firing). Furthermore, since the thermal expansion coefficient differs greatly between silicon and aluminum, a large internal stress is generated in the silicon substrate during the heat treatment (firing) and cooling for forming the aluminum electrode on the silicon substrate. This large internal stress causes damage to crystal grain boundaries, increase of crystal defects, and warpage.
  • an aluminum paste is applied to a part of the surface opposite to the light receiving surface of the silicon substrate (hereinafter also referred to as “back surface”) to partially form a p + -type diffusion layer and an aluminum electrode.
  • a point contact technique has been proposed (see, for example, Patent Document 1).
  • a SiO 2 film or the like as a back surface passivation layer (see, for example, Patent Document 2).
  • the passivation effect by providing such a SiO 2 film is exhibited by the action of terminating the dangling bonds of silicon atoms in the back surface layer portion of the silicon substrate and reducing the surface state density that causes recombination.
  • Such a passivation effect is generally called a field effect, and an aluminum oxide (Al 2 O 3 ) film or the like has been proposed as a material having a negative fixed charge (see, for example, Patent Document 3).
  • Such a passivation layer is generally formed by a method such as an ALD (Atomic Layer Deposition) method or a CVD (Chemical Vapor Deposition) method (for example, see Non-Patent Document 1).
  • Non-Patent Document 1 since the method described in Non-Patent Document 1 includes a complicated manufacturing process such as vapor deposition, it may be difficult to improve productivity.
  • the inventors have examined a composition for forming a passivation layer containing a specific metal compound as a simple method for forming a passivation layer on a semiconductor substrate.
  • the passivation layer can be formed on the semiconductor substrate by a simple method such as a printing method.
  • composition for forming a passivation layer there is a demand for a composition capable of forming a passivation layer which is suppressed in cracking or crack generation and has an excellent passivation effect by a simple method.
  • One embodiment of the present invention has been made in view of the above circumstances, and provides a composition for forming a passivation layer capable of forming a passivation layer having good film quality and excellent passivation effect by a simple method.
  • the task is to do.
  • Another object of one embodiment of the present invention is to provide a semiconductor substrate with a passivation layer, a solar cell element, and a solar cell including a passivation layer that has favorable film quality and an excellent passivation effect.
  • Bi (OR 1 ) m (I) [R 1 independently represents an alkyl group, an aryl group, or an acyl group. m represents 3 or 5. ]
  • M represents at least one selected from the group consisting of Nb, Ta, VO, Y, and Hf.
  • R 6 each independently represents an alkyl group, an aryl group or an acyl group.
  • l represents the valence of M.
  • composition for forming a passivation layer according to ⁇ 4> or ⁇ 5> comprising a hydrolyzate of the compound represented by the general formula (III).
  • a passivation layer-attached semiconductor substrate ⁇ 8> forming a composition layer by applying the passivation layer forming composition according to any one of ⁇ 1> to ⁇ 6> to at least a part of at least one surface of the semiconductor substrate; And a step of forming a passivation layer by heat-treating the composition layer.
  • a solar cell element comprising: a passivation layer that is a heat-treated product of the composition for forming a passivation layer according to claim 1; and an electrode disposed on at least one of the p-type layer and the n-type layer.
  • ⁇ 10> The passivation according to any one of ⁇ 1> to ⁇ 6>, wherein at least part of at least one surface of a semiconductor substrate having a pn junction formed by pn junction of a p-type layer and an n-type layer Applying a layer forming composition to form a composition layer; heat-treating the composition layer to form a passivation layer; and on at least one of the p-type layer and the n-type layer And a step of arranging the electrodes.
  • a solar cell comprising the solar cell element according to ⁇ 9>, and a wiring material disposed on the electrode of the solar cell element.
  • a composition for forming a passivation layer capable of forming a passivation layer having good film quality and excellent passivation effect by a simple technique.
  • a semiconductor substrate with a passivation layer, a solar cell element, and a solar cell including a passivation layer that has a good film quality and an excellent passivation effect are provided. it can.
  • the composition for forming a passivation layer of the present invention a semiconductor substrate with a passivation layer and a method for producing the same, a solar cell element and a method for producing the same, and a mode for carrying out the solar cell will be described in detail.
  • the present invention is not limited to the following embodiments.
  • the constituent elements including element steps and the like) are not essential unless explicitly specified, unless otherwise clearly considered essential in principle.
  • the term “process” is not limited to an independent process, and is included in this term if the purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the content rate or content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total content or content of substances.
  • the term “layer” includes a configuration formed in a part in addition to a configuration formed in the entire surface when observed as a plan view. Further, in this specification, “layer” may be referred to as “film”.
  • the passivation layer in the present embodiment refers to a layer having an effect of suppressing recombination of carriers generated in the semiconductor (hereinafter sometimes referred to as a passivation effect).
  • a passivation layer is formed to terminate defects (dangling bonds) on the semiconductor surface, and the passivation layer has a fixed charge. Examples include a method of bending a band, and the passivation layer may have an effect other than the above as necessary.
  • there are effects such as protecting the surface of a semiconductor and functioning as an antireflection film by having a desired refractive index.
  • film quality means the quality of whether or not the film is in an appropriate state for exhibiting a passivation effect.
  • the passivation effect of the film is not impaired, and the in-plane uniformity is excellent.
  • a film with good film quality is excellent in film thickness uniformity, the film density and refractive index are excellent in the plane and in the thickness direction, and cracks, cracks or peeling are suppressed, etc. It is preferable to have the following characteristics.
  • the film quality can be easily evaluated by a commonly used observation method.
  • a film that does not have cracks, cracks, or peeling, or a film that has relatively few cracks, cracks, or peeling can be evaluated as having good film quality.
  • it can evaluate in detail with the physical-property evaluation method of the thin film used normally. For example, it is possible to measure the film thickness and refractive index at a plurality of points in the surface by an ordinary method using an automatic ellipsometer, and to evaluate that the film quality is better as the standard deviation of the film thickness and refractive index values is smaller.
  • composition for forming a passivation layer of the present embodiment contains a compound represented by the following general formula (I) (hereinafter also referred to as “compound of formula (I)”).
  • each R 1 independently represents an alkyl group, an aryl group, or an acyl group.
  • m represents 3 or 5.
  • composition for forming a passivation layer contains the compound of formula (I), it is possible to form a passivation layer having a good film quality and an excellent passivation effect by a simple technique.
  • the composition for forming a passivation layer contains the compound of formula (I), the passivation effect is easily maintained even after a process such as high temperature and vacuum after the formation of the passivation layer.
  • the passivation effect of a semiconductor substrate refers to an effective lifetime of minority carriers in a semiconductor substrate on which a passivation layer is formed by using a device such as WT-2000PVN manufactured by Nippon Semilab Co., Ltd. It can be evaluated by measuring by the method.
  • the effective lifetime ⁇ is expressed by the following equation (A) by the bulk lifetime ⁇ b inside the semiconductor substrate and the surface lifetime ⁇ s of the semiconductor substrate surface.
  • ⁇ s becomes long, resulting in a long effective lifetime ⁇ .
  • the bulk lifetime ⁇ b is increased and the effective lifetime ⁇ is increased. That is, by measuring the effective lifetime ⁇ , the interface characteristics between the passivation layer and the semiconductor substrate and the internal characteristics of the semiconductor substrate such as dangling bonds can be evaluated.
  • composition for forming a passivation layer of the present embodiment contains a compound represented by the general formula (I) (compound of formula (I)).
  • a passivation layer having an excellent passivation effect can be formed. The reason can be considered as follows.
  • the composition for formation of a passivation layer may contain 1 type of compounds of Formula (I), and may contain 2 or more types.
  • Bismuth oxide (Bi 2 O 3 or Bi 2 O 5 ) formed by heat-treating (firing) a composition for forming a passivation layer containing a compound of formula (I) has defects of bismuth atoms or oxygen atoms. It is considered that a large negative fixed charge is likely to be generated. This fixed charge generates an electric field in the vicinity of the interface of the semiconductor substrate, so that the concentration of minority carriers can be reduced. As a result, the carrier recombination rate at the interface is suppressed, and an excellent passivation effect is obtained. It is done.
  • the state of the passivation layer that generates a fixed charge on the semiconductor substrate a cross section of the semiconductor substrate is observed with a scanning transmission electron microscope (STEM, Scanning Transmission Electron Microscope), and electron energy loss spectroscopy (EELS, Electron) is observed. This can be confirmed by examining the binding mode by analysis of Energy Loss Spectroscopy. Further, by measuring an X-ray diffraction spectrum (XRD, X-ray diffraction), the crystal phase near the interface of the passivation layer can be confirmed. Furthermore, the fixed charge of the passivation layer can be evaluated by a CV method (Capacitance Voltage measurement).
  • each R 1 independently represents an alkyl group, an aryl group, or an acyl group.
  • m represents 3 or 5.
  • R 1 is preferably independently an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an acyl group having 1 to 10 carbon atoms.
  • the alkyl group represented by R 1 may be linear or branched.
  • Each of the alkyl group and aryl group represented by R 1 may have a substituent or may be unsubstituted, and is preferably unsubstituted.
  • m is preferably 3.
  • Examples of the substituent for the alkyl group include an amino group, a hydroxy group, a carboxy group, a sulfo group, and a nitro group.
  • Examples of the substituent for the aryl group include a methyl group, an ethyl group, an isopropyl group, an amino group, a hydroxy group, a carboxy group, a sulfo group, and a nitro group.
  • the acyl group represented by R 1 includes a carbonyl group moiety and a hydrogen atom directly bonded to a carbon atom of the alkyl group moiety, aryl group moiety or carbonyl group moiety.
  • the alkyl group moiety in the acyl group represented by R 1 may be linear or branched.
  • the alkyl group part and the aryl group part in the acyl group represented by R 1 may have a substituent, may be unsubstituted, and are preferably unsubstituted.
  • substituent of the alkyl group moiety in the acyl group represented by R 1 include an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, and a phenyl group, and an aryl group in the acyl group represented by R 1.
  • Examples of the substituent of the group part include a methyl group, an ethyl group, an isopropyl group, an amino group, a hydroxy group, a carboxy group, a sulfo group, and a nitro group.
  • the carbon number of the alkyl group, aryl group, and acyl group represented by R 1 does not include the carbon number of the substituent.
  • Specific examples of the alkyl group represented by R 1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, and an n-hexyl group.
  • R 1 N-octyl group, 2-ethylhexyl group, 3-ethylhexyl group and the like.
  • aryl group represented by R 1 include a phenyl group.
  • acyl group represented by R 1 include a formyl group, an acetyl group, a benzoyl group, and a 2-ethylhexanoyl group.
  • R 1 is preferably an acyl group from the viewpoint of storage stability.
  • the state of the compound of formula (I) may be solid or liquid at 25 ° C.
  • an aluminum oxide precursor or a compound represented by the general formula (III) contained as necessary the compound of the formula (I) is: It is preferably liquid at 25 ° C.
  • the compound of formula (I) include bismuth (III) acetate, bismuth trishexanoate, bismuth tris (2-ethylhexanoate), bismuth trisoctanoate, bismuth tris (2,2-dimethyloctanoate), Examples thereof include bismuth trisneodecanoate and bismuth isopropoxide. Of these, tris (2-ethylhexanoic acid) bismuth is preferred as the compound of formula (I).
  • the compound of formula (I) may be prepared or commercially available.
  • Examples of commercially available products include tris (2-ethylhexanoic acid) bismuth manufactured by Amax Co., Ltd.
  • the compound of formula (I) is prepared by reacting a bismuth halide with an alcohol in the presence of an inert organic solvent, and further adding ammonia or amines to extract the halogen (Japanese Patent Laid-Open No. 63-227593). And a known production method such as JP-A-3-291247).
  • a part of the compound of formula (I) may be contained in the composition for forming a passivation layer as a compound having a chelate structure formed by mixing with a compound having a specific structure having two carbonyl groups described later.
  • the presence of the alkoxide structure in the compound of formula (I) can be confirmed by a commonly used analytical method. For example, it can be confirmed using an infrared spectrum, a nuclear magnetic resonance spectrum, a melting point, or the like.
  • the content of the compound of the formula (I) contained in the composition for forming a passivation layer can be appropriately selected as necessary.
  • the content of the compound of formula (I) is preferably, for example, 1% by mass to 80% by mass with respect to the total mass of the composition for forming a passivation layer, from the viewpoint of the passivation effect, and preferably 3% by mass to 50% by mass. %, More preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 20% by mass.
  • the content of the compound of formula (I) is not particularly limited.
  • the content of the compound of formula (I) in the composition for forming a passivation layer when the total content of the compound of formula (I) and the aluminum oxide precursor is 100% by mass is, for example, 0.5 mass. % To 90% by mass, preferably 1% to 75% by mass, more preferably 2% to 70% by mass, and 3% to 70% by mass. Particularly preferred.
  • the content of the compound of formula (I) By setting the content of the compound of formula (I) to 0.5% by mass or more, the passivation effect tends to be improved.
  • composition for forming a passivation layer may contain water. Further, the composition for forming a passivation layer may contain a hydrolyzate of the compound of formula (I).
  • the composition for forming a passivation layer preferably contains a compound of formula (I) and water.
  • a hydrolyzate of the compound of formula (I) is formed, and the hydrolyzate of the compound of formula (I) is considered to form a network between metal compounds. Further, it is considered that this network is easily broken when the composition for forming a passivation layer is flowing, and is re-formed when the composition becomes stationary again.
  • This network increases the viscosity when the composition for forming a passivation layer is stationary, and decreases the viscosity when the composition is flowing. As a result, it is considered that the viscosity ratio at the high shear rate and the low shear rate of the composition for forming a passivation layer, that is, the thixotropy, is improved, and the thixotropy necessary for pattern formation is expressed.
  • the thixotropy is improved by allowing water to act on the compound of formula (I), and the composition for forming a passivation layer is applied to a semiconductor substrate. Shape stability is further improved, and a passivation layer can be selectively formed at a desired position in a desired shape in a region where the composition layer is formed. Therefore, in the composition for forming a passivation layer containing water, in order to express desired thixotropy, at least one of a thixotropic agent and a resin to be described later (hereinafter, at least one of the thixotropic agent and the resin may be referred to as a thixotropic agent). Even if a thixotropic agent or the like is used, the amount added can be reduced as compared with the conventional passivation layer-forming composition.
  • the thixotropic agent When forming a passivation layer using a composition for forming a passivation layer containing a thixotropic agent composed of an organic substance, the thixotropic agent is thermally decomposed and scattered from the passivation layer through a degreasing process. Become. However, a thermal decomposition product such as a thixotropic agent may remain as an impurity in the passivation layer even after a degreasing process, and the remaining thermal decomposition product such as a thixotropic agent may affect the characteristics of the passivation layer.
  • the thixotropic agent when forming a passivation layer using a composition for forming a passivation layer containing a thixotropic agent composed of an inorganic substance, the thixotropic agent may not be scattered and remain in the passivation layer even after a heat treatment (firing) step. is there. The remaining thixotropic agent may affect the properties of the passivation layer.
  • a composition for forming a passivation layer containing water water or a hydrolyzate of the compound of formula (I) behaves as a thixotropic agent when water acts on the compound of formula (I).
  • Water is more likely to scatter from the passivation layer than a conventional thixotropic agent or the like in a heat treatment (firing) step or the like that is performed when the passivation layer is formed using the passivation layer forming composition. For this reason, it is difficult to cause a decrease in the passivation effect of the passivation layer due to the presence of the residue in the passivation layer.
  • the composition for forming a passivation layer contains water, it is possible to form a passivation layer having excellent pattern forming properties and excellent passivation effect by a simple technique. Moreover, a passivation layer having a desired shape can be formed by using a composition for forming a passivation layer having excellent pattern formability. This makes it possible to manufacture an excellent semiconductor substrate with a passivation layer, a solar cell element, and a solar cell.
  • the water state may be solid or liquid. From the viewpoint of miscibility with the compound of formula (I), water is preferably a liquid.
  • the content of water contained in the composition for forming a passivation layer can be appropriately selected as necessary.
  • the water content is preferably, for example, 0.01% by mass or more with respect to the total mass of the composition for forming a passivation layer.
  • the content is more preferably 03% by mass or more, further preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more.
  • the content rate of water is 80 mass% or less with respect to the total mass of the composition for passivation layer formation from a viewpoint of pattern formation property and a passivation effect, for example, and it is 70 mass% or less. Is more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
  • the compound of formula (I) (when the composition for forming a passivation layer contains an aluminum oxide precursor, a compound of formula (III), a silicon compound, etc., the compound of formula (I) and the total thereof)
  • the amount of water that has acted on can be calculated from the amount of alcohol or carboxylic acid liberated from the compound of formula (I).
  • alcohol or carboxylic acid is liberated from the compound of formula (I).
  • the amount of this free alcohol or carboxylic acid is proportional to the number of functional groups of the compound of formula (I) to which water has acted.
  • the amount of water acting on the compound of formula (I) can be calculated.
  • Measurement of the amount of liberated alcohol or carboxylic acid can be confirmed using, for example, gas chromatography mass spectrometry (GC-MS).
  • the content of alcohol or carboxylic acid contained in the composition for forming a passivation layer is, for example, preferably 0.5% by mass to 70% by mass, more preferably 1% by mass to 60% by mass. More preferably, the content is from 50% by mass to 50% by mass.
  • the composition for forming a passivation layer may contain at least one hydrolyzate of the compound of formula (I), and if necessary, contains at least one hydrolyzate of an aluminum oxide precursor described later. It may contain, and may contain at least 1 sort (s) of hydrolyzate of the formula (III) compound mentioned later.
  • the hydrolyzate of the compound of formula (I) may contain a dehydration condensate of the hydrolyzate of the compound of formula (I), and the hydrolyzate of the aluminum oxide precursor includes an aluminum oxide precursor.
  • the hydrolyzate of the hydrolyzate of formula (III) may be contained, and the hydrolyzate of the compound of formula (III) may contain the dehydration condensate of the hydrolyzate of the compound of formula (III).
  • the content of the compound of formula (I) is the total content of the compound of formula (I) and the hydrolyzate of the compound of formula (I) in the composition for forming a passivation layer. is there.
  • the content of the aluminum oxide precursor described later is the total content of the aluminum oxide precursor and the hydrolyzate of the aluminum oxide precursor in the composition for forming the passivation layer. It is.
  • the content of the compound of formula (III) described later is the sum of the compound of formula (III) and the hydrolyzate of the compound of formula (III) in the composition for forming a passivation layer. It is the content rate of. Furthermore, in the composition for forming a passivation layer containing water, the content of the silicon compound is the total content of the silicon compound and the hydrolyzate of the silicon compound in the composition for forming the passivation layer.
  • the composition for forming a passivation layer may contain an aluminum oxide precursor.
  • the aluminum oxide precursor is not particularly limited as long as it can produce aluminum oxide by heat treatment (firing).
  • the composition for forming a passivation layer may contain one type of aluminum oxide precursor or two or more types.
  • the aluminum oxide precursor becomes aluminum oxide (Al 2 O 3 ) by heat treatment (firing). At this time, the formed aluminum oxide tends to be in an amorphous state, and a four-coordinate aluminum oxide layer is easily formed in the vicinity of the interface with the semiconductor substrate. It is considered that due to the four-coordinate aluminum oxide layer, a large negative fixed charge can be provided in the vicinity of the interface with the semiconductor substrate. Thereby, an electric field is generated in the vicinity of the interface with the semiconductor substrate, and the concentration of minority carriers can be reduced. As a result, it is considered that the carrier recombination rate at the interface with the semiconductor substrate is suppressed, and an excellent passivation effect is obtained.
  • the passivation effect becomes higher due to the respective effects in the passivation layer.
  • physical properties such as reactivity and vapor pressure are improved
  • the denseness of the passivation layer as a heat-treated product (baked product) is improved, and as a result, the passivation effect is further enhanced.
  • the denseness of the passivation layer can be evaluated visually by using a transmission electron microscope, from the contrast of the observed image, whether or not unevenness and voids are generated.
  • the aluminum oxide precursor may be liquid or solid. From the viewpoint of the passivation effect and storage stability, when using a liquid medium with stability at normal temperature (for example, 25 ° C.), use an aluminum oxide precursor having good solubility or dispersibility in the liquid medium. Is desirable. By using such an aluminum oxide precursor, the homogeneity of the formed passivation layer is further improved, and a desired passivation effect tends to be stably obtained.
  • an organic aluminum oxide precursor is preferably used, and examples thereof include a compound represented by the following general formula (II) (hereinafter also referred to as “specific aluminum compound”).
  • each R 2 independently represents an alkyl group.
  • n represents an integer of 0 to 3.
  • X 2 and X 3 each independently represent an oxygen atom or a methylene group.
  • R 3 , R 4 and R 5 each independently represents a hydrogen atom or an alkyl group.
  • a plurality of groups represented by the same symbol may be the same or different.
  • each R 2 independently represents an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group represented by R 2 may be linear or branched.
  • the alkyl group represented by R 2 may have a substituent or may be unsubstituted, and is preferably unsubstituted. Examples of the substituent for the alkyl group include an amino group, a hydroxy group, a carboxy group, a sulfo group, and a nitro group. Note that the carbon number of the alkyl group represented by R 2 does not include the carbon number of the substituent.
  • the alkyl group represented by R 2 is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and is an unsubstituted alkyl group having 1 to 4 carbon atoms from the viewpoint of storage stability and a passivation effect. It is more preferable.
  • alkyl group represented by R 2 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and n-hexyl group. N-octyl group, 2-ethylhexyl group, 3-ethylhexyl group and the like.
  • n represents an integer of 0 to 3. It is preferably an integer of 1 to 3, more preferably 1 or 3, from the viewpoint of suppressing occurrence of problems such as gelation and ensuring storage stability over time, and 1 from the viewpoint of solubility. More preferably it is.
  • X 2 and X 3 in the general formula (II) each independently represent an oxygen atom or a methylene group. From the viewpoint of storage stability, at least one of X 2 and X 3 is preferably an oxygen atom.
  • R 3 , R 4 and R 5 in the general formula (II) each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or 1 carbon atom. More preferably, it is an alkyl group of ⁇ 4.
  • the alkyl group represented by R 3 , R 4 and R 5 may be linear or branched.
  • the alkyl group represented by R 3 , R 4 and R 5 may have a substituent or may be unsubstituted, and is preferably unsubstituted.
  • Examples of the substituent for the alkyl group include an amino group, a hydroxy group, a carboxy group, a sulfo group, and a nitro group. Note that the carbon number of the alkyl group represented by R 3 , R 4, and R 5 does not include the carbon number of the substituent.
  • R 3 and R 4 in the general formula (II) are preferably each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms. Or it is more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms.
  • R 5 in the general formula (II) is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms from the viewpoint of storage stability and a passivation effect, and is preferably a hydrogen atom or a carbon atom having 1 to 4 carbon atoms. It is more preferably an unsubstituted alkyl group.
  • alkyl group represented by R 3 , R 4 and R 5 in the general formula (II) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group.
  • the specific aluminum compound is a compound in which n in the general formula (II) is 0 and R 2 is each independently an alkyl group having 1 to 4 carbon atoms from the viewpoint of storage stability and a passivation effect, N in the formula (II) is an integer of 1 to 3, R 2 is each independently an alkyl group having 1 to 4 carbon atoms, and at least one of X 2 and X 3 is an oxygen atom, R 3 and R 4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferable that at least one selected.
  • the specific aluminum compound is a compound in which n in the general formula (II) is 0 and R 2 is each independently an unsubstituted alkyl group having 1 to 4 carbon atoms, and the general formula (II) ) Is an integer of 1 to 3, R 2 is each independently an unsubstituted alkyl group having 1 to 4 carbon atoms, and at least one of X 2 and X 3 is an oxygen atom, When R 3 or R 4 bonded to the oxygen atom is an alkyl group having 1 to 4 carbon atoms and X 2 or X 3 is a methylene group, R 3 or R 4 bonded to the methylene group is a hydrogen atom, , R 5 is at least one selected from the group consisting of compounds each having a hydrogen atom.
  • n in the general formula (II) is an integer of 1 to 3
  • R 5 is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A certain compound is preferable.
  • n 0
  • trimethoxyaluminum triethoxyaluminum, triisopropoxyaluminum, trisec-butoxyaluminum, monosec- Examples include butoxy-diisopropoxyaluminum, tritert-butoxyaluminum, and tri-n-butoxyaluminum.
  • Specific examples of the specific aluminum compound represented by the general formula (II) where n is an integer of 1 to 3 include aluminum ethyl acetoacetate diisopropylate, aluminum methylacetoacetate diisopropylate, aluminum tris (ethylacetoacetate). ), Aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), and the like.
  • the specific aluminum compound represented by the general formula (II) and n is an integer of 1 to 3 may be either prepared or commercially available.
  • Commercially available products include, for example, trade names of Kawaken Fine Chemical Co., Ltd., ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, aluminum chelate M, aluminum chelate D, and aluminum chelate A (W). Can be mentioned.
  • the specific aluminum compound represented by the general formula (II) and n is an integer of 1 to 3 is prepared by mixing an aluminum trialkoxide and a compound having a specific structure having two carbonyl groups described later. Can do. A commercially available aluminum chelate compound may also be used. When an aluminum trialkoxide and a compound having a specific structure having two carbonyl groups are mixed, at least a part of the alkoxy group of the aluminum trialkoxide is substituted with a compound having a specific structure to form an aluminum chelate structure. At this time, if necessary, a liquid medium may be present, and heat treatment, addition of a catalyst, and the like may be performed.
  • the stability of the specific aluminum compound to hydrolysis and polymerization reaction is improved, and the storage stability of the composition for forming a passivation layer containing this is further improved. To do.
  • the compound having a specific structure having two carbonyl groups is at least one selected from the group consisting of a ⁇ -diketone compound, a ⁇ -ketoester compound, and a malonic acid diester from the viewpoint of reactivity and storage stability. preferable.
  • Specific examples of the compound having a specific structure having two carbonyl groups include acetylacetone, 3-methyl-2,4-pentanedione, 2,3-pentanedione, 3-ethyl-2,4-pentanedione, and 3-butyl.
  • ⁇ -diketone compound methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, isobutyl acetoacetate, n-butyl acetoacetate, t-butyl acetoacetate, n-pentyl acetoacetate, isopentyl acetoacetate, N-hexyl acetoacetate, n-octyl acetoacetate, n-heptyl acetoacetate, 3-pentyl acetoacetate, 2-acetate Ethyl luheptanoate, ethyl 2-methylacetoacetate, ethyl 2-butylacetoacetate, ethyl hexylacetoacetate, ethyl 4,4-dimethyl-3-oxovalerate, ethyl 4-methyl-3-oxovalerate, ethyl 2-e
  • the number of aluminum chelate structures is not particularly limited as long as it is 1 to 3. Among these, 1 or 3 is preferable from the viewpoint of storage stability, and 1 is more preferable from the viewpoint of solubility.
  • the number of aluminum chelate structures can be controlled, for example, by appropriately adjusting the ratio of mixing aluminum trialkoxide and a compound having a specific structure having two carbonyl groups. Moreover, you may select suitably the compound which has a desired structure from a commercially available aluminum chelate compound.
  • the specific aluminum compound is specifically at least one selected from the group consisting of aluminum ethyl acetoacetate diisopropylate and triisopropoxyaluminum from the viewpoint of the passivation effect and compatibility with the solvent contained as necessary. It is preferable that aluminum ethyl acetoacetate diisopropylate is included.
  • the presence of the aluminum chelate structure and the presence of the alkoxide structure in the specific aluminum compound can be confirmed by a commonly used analysis method. For example, it can be confirmed using an infrared spectrum, a nuclear magnetic resonance spectrum, a melting point, or the like.
  • the content of the specific aluminum compound in the aluminum oxide precursor is, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and 95 More preferably, it is at least mass%.
  • the content of the aluminum oxide precursor in the composition for forming a passivation layer can be appropriately selected as necessary.
  • the content of the aluminum oxide precursor is preferably, for example, 0.1% by mass to 60% by mass with respect to the total mass of the composition for forming a passivation layer from the viewpoint of storage stability and a passivation effect. It is more preferably from 5% by mass to 55% by mass, further preferably from 1% by mass to 50% by mass, and particularly preferably from 1% by mass to 45% by mass.
  • the content of the aluminum oxide precursor is not particularly limited.
  • the content of the aluminum oxide precursor in the composition for forming a passivation layer when the total content of the compound of formula (I) and the aluminum oxide precursor is 100% by mass is, for example, 10% by mass to 99%. 0.5% by mass, more preferably 25% by mass to 99% by mass, further preferably 30% by mass to 98% by mass, and particularly preferably 30% by mass to 97% by mass. preferable.
  • the content of the aluminum oxide precursor By setting the content of the aluminum oxide precursor to 10% by mass or more, the passivation effect tends to be improved.
  • the composition for forming a passivation layer may contain a compound represented by the following general formula (III) (hereinafter also referred to as “compound of formula (III)”).
  • compound of formula (III) When the composition for forming a passivation layer contains the compound of formula (III), a passivation layer having an excellent passivation effect can be formed.
  • the composition for formation of a passivation layer may contain 1 type of compounds of Formula (III), and may contain 2 or more types.
  • a larger negative fixed charge is developed, and the passivation effect tends to be further improved.
  • a composite oxide having a large refractive index tends to be generated.
  • the passivation layer containing a complex oxide with a high refractive index improves the power generation performance because sunlight is refracted at the interface with the semiconductor substrate and re-enters the solar cells while preventing the sunlight from escaping to the back side. Tend to.
  • M is at least one selected from the group consisting of Nb, Ta, VO, Y, and Hf.
  • the passivation effect, the pattern forming property of the composition for forming a passivation layer, and the formation of the passivation layer M is preferably at least one selected from the group consisting of Nb, Ta, and Y from the viewpoint of workability when preparing the composition for use, and from the viewpoint of the passivation effect of the composition for forming a passivation layer. More preferably, it is Nb.
  • each R 6 independently represents an alkyl group, an aryl group, or an acyl group, and is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
  • An acyl group is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.
  • the alkyl group represented by R 6 may be linear or branched.
  • the alkyl group and aryl group represented by R 6 may have a substituent or may be unsubstituted, and is preferably unsubstituted.
  • Examples of the substituent for the alkyl group include an amino group, a hydroxy group, a carboxy group, a sulfo group, and a nitro group.
  • Examples of the substituent for the aryl group include a methyl group, an ethyl group, an isopropyl group, an amino group, a hydroxy group, a carboxy group, a sulfo group, and a nitro group.
  • the acyl group represented by R 6 includes a carbonyl group part and a hydrogen atom directly bonded to a carbon atom of the alkyl group part, aryl group part or carbonyl group part.
  • the alkyl group moiety in the acyl group represented by R 6 may be linear or branched.
  • the alkyl group part and the aryl group part in the acyl group represented by R 6 may have a substituent, may be unsubstituted, or are preferably unsubstituted.
  • substituent of the alkyl group moiety in the acyl group represented by R 6 include an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, and a phenyl group, and an aryl group in the acyl group represented by R 6.
  • Examples of the substituent of the group part include a methyl group, an ethyl group, an isopropyl group, an amino group, a hydroxy group, a carboxy group, a sulfo group, and a nitro group.
  • the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group, aryl group, and acyl group represented by R 6 .
  • Specific examples of the alkyl group represented by R 6 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and n-hexyl group.
  • R 6 N-octyl group, 2-ethylhexyl group, 3-ethylhexyl group and the like.
  • aryl group represented by R 6 include a phenyl group.
  • acyl group represented by R 6 include formyl group, acetyl group, benzoyl group, 2-ethylhexanoyl group and the like.
  • R 6 is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, from the viewpoint of the passivation effect.
  • l represents the valence of M.
  • M when M is Nb, l is preferably 5, and when M is Ta, l is preferably 5, and M is VO.
  • l is preferably 3, 1 is preferably 3 when M is Y, and 1 is preferably 4 when M is Hf.
  • M is preferably at least one selected from the group consisting of Nb, Ta and Y, and R 6 is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms.
  • the state of the compound of formula (III) may be solid or liquid at 25 ° C.
  • the compound of formula (III) is preferably liquid at 25 ° C.
  • the compound of formula (III) in which R 6 is an alkyl group is specifically niobium methoxide, niobium ethoxide, niobium isopropoxide, niobium n-propoxide, niobium n-butoxide, niobium t-butoxide, niobium iso Butoxide, Tantalum methoxide, Tantalum ethoxide, Tantalum isopropoxide, Tantalum n-propoxide, Tantalum n-butoxide, Tantalum t-butoxide, Tantalum isobutoxide, Yttrium methoxide, Yttrium ethoxide, Yttrium isopropoxide, Yttrium n -Propoxide, yttrium n-butoxide, yttrium t-butoxide, yttrium isobutoxide, vanadium oxymethoxide,
  • R 6 is an aryl group
  • Specific examples of the compound of formula (III) in which R 6 is an aryl group include niobium phenoxide, tantalum phenoxide, yttrium phenoxide, hafnium phenoxide and the like.
  • Compounds of formula (III) in which R 6 is an acyl group are niobium formate, niobium acetate, niobium 2-ethylhexanoate, tantalum acetate, tantalum 2-ethylhexanoate, yttrium formate, yttrium acetate, yttrium 2-ethylhexanoate, Examples include hafnium formate, hafnium acetate, and hafnium 2-ethylhexanoate.
  • the compound of formula (III) may be either prepared or commercially available.
  • Commercially available products include pentamethoxy niobium, pentaethoxy niobium, pentaisopropoxy niobium, penta-n-propoxy niobium, pentaisobutoxy niobium, penta-n-butoxy niobium, penta-sec-butoxy from High Purity Chemical Laboratory Co., Ltd.
  • Niobium pentamethoxy tantalum, pentaethoxy tantalum, pentaisopropoxy tantalum, penta-n-propoxy tantalum, pentaisobutoxy tantalum, penta-n-butoxy tantalum, penta-sec-butoxy tantalum, penta-t-butoxy tantalum, vanadium ( V) trimethoxide oxide, vanadium (V) triethoxy oxide, vanadium (V) triisopropoxide oxide, vanadium (V) tri-n-propoxide oxide, vanadium (V) triisobutoxy Oxide, vanadium (V) tri-n-butoxide oxide, vanadium (V) tri-sec-butoxide oxide, vanadium (V) tri-t-butoxide oxide, triisopropoxy yttrium, tri-n-butoxy yttrium, tetramethoxyhafnium , Tetraethoxyhafnium, t
  • a halide of a specific metal (M) and an alcohol are reacted in the presence of an inert organic solvent, and ammonia or an amine is added to extract a halogen (specialty).
  • Known manufacturing methods such as Japanese Utility Model Laid-Open No. 63-227593 and Japanese Patent Laid-Open No. 3-291247) can be used.
  • a part of the compound of formula (III) is contained in the composition for forming a passivation layer as a compound in which a chelate structure is formed by mixing with a compound having a specific structure having two carbonyl groups as in the compound of formula (I). May be.
  • the presence of the alkoxide structure in the compound of formula (III) can be confirmed by a commonly used analysis method. For example, it can be confirmed using an infrared spectrum, a nuclear magnetic resonance spectrum, a melting point, or the like.
  • the content of the compound of formula (III) contained in the composition for forming a passivation layer can be appropriately selected as necessary.
  • the content of the compound of formula (III) is preferably 0.1% by mass to 50% by mass with respect to the total mass of the composition for forming a passivation layer, for example, 0.5% by mass. % To 30% by mass is more preferable, 1% to 20% by mass is further preferable, and 1% to 10% by mass is particularly preferable.
  • the composition for forming a passivation layer may contain a silicon compound.
  • the silicon compound is physically or chemically interacted or chemically bonded with the compound of formula (I), the aluminum oxide precursor, the compound of formula (III), the resin, the liquid medium, etc. in the composition for forming a passivation layer,
  • the surface tension of the composition for forming a passivation layer can be controlled. Thereby, the thickness nonuniformity of the composition layer which is a coating film is suppressed, and the variation in the thickness of the passivation layer formed is suppressed.
  • the generation of voids in the heat-treated product layer (baked product layer) of the composition for forming a passivation layer is suppressed, the density of the passivation layer is improved, and a homogeneous passivation layer is formed. Is obtained.
  • the silicon compound is not particularly limited as long as it contains a silicon atom in the molecule.
  • the silicon compound is preferably a compound in which an oxygen atom is bonded to a silicon atom from the viewpoint of easy preparation of the composition for forming a passivation layer.
  • the compound in which an oxygen atom is bonded to a silicon atom may form a complex with at least one selected from the group consisting of an organic compound and an inorganic compound.
  • Specific examples of the silicon compound include silicon alkoxides, silicate compounds, and silicone oils and siloxane resins that are compounds having a siloxane bond. Among these, silicon alkoxides, silicate compounds, and silicone oils are preferable.
  • the silicone oil may be a copolymer of a compound having a siloxane bond and another compound.
  • the silicon alkoxide and silicate compound may be oligomers.
  • the oligomer of a silicate compound is a silicate compound represented by the following general formula (IV).
  • Si k O k-1 (R 7 O) 2 (k + 1) (IV)
  • R 7 represents an alkyl group having 1 to 8 carbon atoms.
  • k represents an integer of 1 to 10.
  • the silicate compound include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, n-pentyl silicate, acetyl silicate and the like.
  • the silicate compound may be an oligomer of a silicate compound, and examples of commercially available products include those commercially available from Fuso Chemical Industry Co., Ltd., Tama Chemical Industry Co., Ltd., Colcoat Co., Ltd. and the like.
  • Specific examples of methyl silicate and oligomers thereof include methyl silicate 51 manufactured by Fuso Chemical Industry Co., Ltd. or Colcoat Co., Ltd., methyl silicate 53A manufactured by Colcoat Co., Ltd., and the like.
  • Specific examples of ethyl silicate and oligomers thereof include ethyl silicate 40 manufactured by Tama Chemical Co., Ltd.
  • ethyl silicate 45 manufactured by Tama Chemical Industry Co., Ltd.
  • ethyl silicate 28 manufactured by Colcoat Co., Ltd.
  • ethyl silicate 48 manufactured by Colcoat Co., Ltd.
  • Specific examples of other silicates and oligomers thereof include N-propyl silicate and N-butyl silicate manufactured by Colcoat Co., Ltd.
  • the silicon compound preferably contains a silicate compound. It is considered that the silicate compound reacts more slowly with the compound of formula (I) in the heat treatment (firing) than the silicon alkoxide, and the reaction can be suppressed to a specific temperature state. Thus, it is assumed that the reaction occurs uniformly, the generation of voids in the heat-treated product layer (baked product layer) is suppressed, and the denseness of the passivation layer is improved.
  • the silicate compound is preferably an ethyl silicate compound or an ethyl silicate oligomer.
  • the plurality of R 7 O groups possessed by the silicate compound may be the same or different.
  • the R 7 O group preferably contains a methoxy group and an ethoxy group.
  • the ratio of the equivalent number of methoxy groups to the equivalent number of ethoxy groups is preferably, for example, 30/70 to 70/30, It is more preferably 40/60 to 60/40, further preferably 45/55 to 55/45, and the number of equivalents of methoxy group and the number of equivalents of ethoxy group are particularly preferably close to equivalent.
  • An example of a silicate compound having approximately equal amounts of methoxy group and ethoxy group is EMS-485 manufactured by Colcoat Co., Ltd.
  • the silicate compound may be used alone or in combination of two or more.
  • the silicate compound may be used in combination with water, a catalyst, a liquid medium, or the like, if necessary.
  • the silicon alkoxide is not particularly limited as long as it has a silicon atom and an alkoxy group bonded to the silicon atom.
  • Specific examples of the silicon alkoxide include compounds represented by the following general formula (V), silane coupling agents, and the like. R n Si (OR 8 ) 4-n (V)
  • R represents an alkyl group or an aryl group, the alkyl group and the aryl group may have a substituent, and R 8 is a saturated or unsaturated group having 1 to 6 carbon atoms.
  • a hydrocarbon group or a hydrocarbon group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms is shown.
  • n represents 1 to 3, and preferably 1 or 2.
  • the alkyl group represented by R in the general formula (V) preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • the aryl group represented by R in the general formula (V) preferably has 6 to 14 carbon atoms, and more preferably a phenyl group.
  • examples of the substituent that the alkyl group represented by R may have include a fluorine atom, a (meth) acryloxy group, a vinyl group, an epoxy group, a styryl group, and an amino group.
  • the amino group may further have a substituent, and examples of the amino group having a substituent include an N-2- (aminoethyl) -3-amino group and an N-phenyl-3-amino group. It is done.
  • Examples of the saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms represented by R 8 in the general formula (V) include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, Examples include cyclohexyl.
  • Examples of the hydrocarbon group having 1 to 6 carbon atoms substituted by an alkoxy group having 1 to 6 carbon atoms represented by R 8 in the general formula (V) include methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl , Methoxypropyl, ethoxypropyl, propoxypropyl and the like.
  • the silicon alkoxide preferably contains a silane coupling agent.
  • the silane coupling agent is not particularly limited as long as it is a compound having a silicon atom, an alkoxy group, and an organic functional group other than the alkoxy group in one molecule.
  • a silane coupling agent may be used individually by 1 type, and may use 2 or more types together.
  • Examples of the silicon alkoxide include the following compounds (a) to (g) containing a silane coupling agent.
  • Silicon alkoxide having (meth) acryloxy group (b) Epoxy group such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Or a silicon alkoxide having a glycidoxy group (c) N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyl Silicon alkoxides having amino groups such as pyrtriethoxysilane (d) Silicon alkoxides having mercapto groups such as 3-mercaptopropyltrimethoxysilane (e) Methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyl
  • the silicon alkoxide preferably includes a silicon alkoxide having an acryloxy group, a methacryloxy group, an epoxy group, an alkyl group, or a trifluoroalkyl group. Silicon alkoxide may be used in combination with water, a catalyst, a liquid medium, or the like, if necessary.
  • silicone oil there is no particular limitation as silicone oil.
  • Specific examples of the silicone oil include dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, and mercapto.
  • Modified silicone oil epoxy modified silicone oil, carboxyl modified silicone oil, higher fatty acid modified silicone oil, carnauba modified silicone oil, amide modified silicone oil, radical reactive group containing silicone oil, terminal reactive silicone oil, ionic group containing silicone oil Etc.
  • the content of the silicon compound is preferably 0.01% by mass to 35% by mass, and preferably 0.05% by mass to 30% by mass with respect to the total mass of the composition for forming a passivation layer. More preferably, it is 0.1% by mass to 20% by mass, and particularly preferably 0.1% by mass to 10% by mass.
  • the content of the silicon compound is 0.01% by mass or more, the surface tension of the composition for forming a passivation layer tends to be reduced and the printability tends to be improved, and the content of the silicon compound is 35% by mass or less. Then, the passivation effect tends to be obtained more sufficiently.
  • the silicon atom content in the composition for forming a passivation layer is preferably 0.001% by mass to 15% by mass, more preferably 0.01% by mass to 10% by mass, and 0.05% by mass. More preferably, the content is from 5% to 5% by mass.
  • the composition for forming a passivation layer may further contain a resin.
  • the shape stability of the composition layer formed by applying the composition for forming a passivation layer on a semiconductor substrate is further improved, and the composition layer is formed as a passivation layer. In the formed region, it can be selectively formed at a desired position in a desired shape.
  • the type of resin is not particularly limited.
  • the resin is preferably a resin whose viscosity can be adjusted in a range where a good pattern can be formed when the composition for forming a passivation layer is applied onto a semiconductor substrate.
  • Specific examples of the resin include polyvinyl alcohol, polyacrylamide, polyacrylamide derivatives, polyvinylamide, polyvinylamide derivatives, polyvinylpyrrolidone, polyethylene oxide, polyethylene oxide derivatives, polysulfonic acid, polyacrylamide alkylsulfonic acid, cellulose, and cellulose derivatives (carboxymethylcellulose).
  • Cellulose ethers such as hydroxyethyl cellulose and ethyl cellulose
  • gelatin gelatin derivatives, starch, starch derivatives, sodium alginate, sodium alginate derivatives, xanthan, xanthan derivatives, guar gum, guar gum derivatives, scleroglucan, scleroglucan derivatives, tragacanth, Tragacanth derivative, dextrin, dextrin derivative, (meta) Acrylic acid resins, and the like (meth) acrylic acid ester resin (alkyl (meth) acrylate resin, dimethylaminoethyl (meth) acrylate resin, etc.), butadiene resins, styrene resins, copolymers thereof. These resins may be used alone or in combination of two or more.
  • (meth) acryl represents at least one of acryl and methacryl
  • (meth) acrylate represents at least one of acrylate and methacrylate.
  • the molecular weight of these resins is not particularly limited, and it is preferable to adjust appropriately in view of the desired viscosity as the composition for forming a passivation layer.
  • the weight average molecular weight of the resin is preferably, for example, 1,000 to 10,000,000, more preferably 1,000 to 5,000,000, from the viewpoint of storage stability and pattern formability. .
  • the weight average molecular weight of resin is calculated
  • the content of the resin in the composition for forming a passivation layer can be appropriately selected as necessary.
  • the resin content is preferably 0.1% by mass to 50% by mass with respect to the total mass of the passivation layer forming composition.
  • the resin content is more preferably 0.2% by mass to 25% by mass, and more preferably 0.5% by mass to 20% by mass. Is more preferable, and 0.5 to 15% by mass is particularly preferable.
  • the thixotropy of the composition is improved by allowing water to act on the compound of formula (I) as described above, in the composition for forming a passivation layer containing water, it is necessary to develop thixotropy with a resin. Is not expensive. Therefore, the content of the resin contained in the composition for forming a passivation layer containing water is, for example, preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and further preferably 0.1% by mass or less. It is particularly preferable that the resin does not substantially contain any resin.
  • a high boiling point material In the composition for forming a passivation layer, a high boiling point material may be used together with or instead of the resin.
  • the high boiling point material is preferably a compound that is easily vaporized when heated and does not need to be degreased.
  • the high boiling point material has a high viscosity so that the shape can be maintained after the composition for forming a passivation layer is applied to the semiconductor substrate.
  • An example of a material that satisfies these conditions is isobornylcyclohexanol.
  • Isobornyl cyclohexanol is commercially available, for example, as “Telsolve MTPH” (Nippon Terpene Chemical Co., Ltd., trade name). Isobornyl cyclohexanol has a high boiling point of 308 ° C. to 318 ° C. When it is removed from the composition layer, it does not need to be degreased by heat treatment (firing) like a resin, but is vaporized by heating. Can be eliminated. For this reason, most of the solvent and isobornyl cyclohexanol contained in the composition for forming a passivation layer as necessary can be removed in the drying step after application on the semiconductor substrate.
  • the content of the high boiling point material is preferably, for example, 3% by mass to 95% by mass with respect to the total mass of the composition for forming a passivation layer. It is more preferably 5% by mass to 90% by mass, and further preferably 7% by mass to 80% by mass.
  • the composition for forming a passivation layer may further contain a liquid medium (solvent or dispersion medium).
  • a liquid medium solvent or dispersion medium
  • the viscosity can be easily adjusted, the impartability is further improved, and a more uniform passivation layer tends to be formed. It does not restrict
  • the liquid medium preferably includes a liquid medium capable of dissolving the compound of formula (I), an aluminum oxide precursor added if necessary, and the compound of formula (III) to form a uniform solution, and at least one of the organic solvents. More preferably it contains a seed.
  • a liquid medium means a medium in a liquid state at room temperature (25 ° C.).
  • liquid medium examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, Ketone solvents such as di-n-propyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone; diethyl ether, methyl ethyl ether, methyl-n-propyl Ether, diisopropyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane, ethylene glycol di
  • Phenol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether Ter, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Examples include glycol monoether solvents such as dipropylene glycol monoethyl ether and tripropylene glycol monomethyl ether; terpene solvents such as terpinene, terpineol, myrcene, alloocimene, limonene, dipentene, pinene, carvone, oximene, and ferrandolene. These liquid media may be used individually by 1 type, and may use 2 or
  • the liquid medium preferably contains at least one selected from the group consisting of a terpene solvent, an ester solvent, and an alcohol solvent from the viewpoint of impartability to a semiconductor substrate and pattern formation, and is selected from the group consisting of a terpene solvent. More preferably, it contains at least one of the above.
  • the content of the liquid medium is determined in consideration of the imparting property, pattern forming property, and storage stability.
  • the content of the liquid medium is 5% by mass to 98% by mass with respect to the total mass of the composition for forming a passivation layer, from the viewpoint of impartability of the composition for forming a passivation layer and pattern formation.
  • the content is preferably 10% by mass to 95% by mass.
  • the composition for forming a passivation layer may further contain at least one of an acidic compound and a basic compound.
  • the content of the acidic compound or the basic compound is, for example, relative to the total mass of the composition for forming a passivation layer In each case, the content is preferably 1% by mass or less, and more preferably 0.1% by mass or less.
  • acidic compounds include Bronsted acid and Lewis acid. Specific examples include inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid.
  • Examples of basic compounds include Bronsted bases and Lewis bases.
  • the basic compound include inorganic bases such as alkali metal hydroxides and alkaline earth metal hydroxides, and organic bases such as trialkylamine and pyridine.
  • the composition for forming a passivation layer comprises Bi, Al, Nb, Ta, V, Y, in addition to the compound of formula (I), an aluminum oxide precursor or a compound of formula (III) contained as necessary, and a silicon compound.
  • other metal compounds containing metal elements other than Hf may be further contained. Examples of other metal compounds include metal alkoxides containing metal elements other than Bi, Al, Nb, Ta, V, Y, and Hf, metal complexes such as chelate complexes, and organometallic compounds.
  • Another metal compound may be used individually by 1 type, or may use 2 or more types together.
  • the composition for forming a passivation layer contains other metal compound, a larger negative fixed charge is developed, and the passivation effect tends to be further improved. Moreover, when the composition for forming a passivation layer containing other metal compounds is heat-treated (fired), a composite oxide having a large refractive index tends to be generated.
  • the passivation layer containing a complex oxide with a high refractive index improves the power generation performance because sunlight is refracted at the interface with the semiconductor substrate and re-enters the solar cells while preventing the sunlight from escaping to the back side. Tend to.
  • the other metal compound preferably contains a metal alkoxide from the viewpoint of the reactivity of the compound of formula (I), the aluminum oxide precursor contained as necessary, the compound of formula (III) and the silicon compound.
  • the metal alkoxide is not particularly limited as long as it is a compound obtained by reacting a metal atom with an alcohol. Specific examples of the metal alkoxide include compounds represented by the following general formula (VI). M 2 (OR 9 ) t (VI)
  • M 2 represents a metal element having a valence of 1 to 7 (excluding Bi, Al, Nb, Ta, V, Y, and Hf).
  • M 2 Li, Na, K , Mg, Ca, Sr, Ba, La, Ti, B, Zr, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, and Examples thereof include at least one metal element selected from the group consisting of Pb.
  • M 2 is Li, Na, K, Mg, Ca, Sr, Ba, La, Ti, B, Zr, Mo, Co, Zn, and It is preferably at least one metal element selected from the group consisting of Pb, more preferably at least one metal element selected from the group consisting of Ti and Zr.
  • R 9 represents a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms.
  • . t represents the valence of M 2.
  • Examples of the group represented by R 9 in the general formula (VI) include the same groups as the group represented by R 8 in the general formula (V).
  • the composition for forming a passivation layer comprises a reaction product of a compound of formula (I) and at least one of an aluminum oxide precursor, a compound of formula (III), a silicon compound, and another metal compound, which is included as necessary. May be included.
  • water may be added to the composition for forming a passivation layer.
  • the aluminum oxide precursor, silicon compound, and other metal compounds included as necessary are alkoxides, hydrolysis progresses by adding water, and thixotropy increases, thereby forming a passivation layer forming composition.
  • the printability of the object can be improved.
  • the composition for forming a passivation layer may further contain other components usually used in the field as necessary, in addition to the components described above.
  • Other components include, for example, thixotropic agents such as organic fillers, inorganic fillers and organic acid salts (water, hydrolyzate of compound of formula (I), hydrolyzate of aluminum oxide precursor and hydrolyzate of compound of formula (III). Excluding decomposition products), wettability improvers, leveling agents, surfactants, plasticizers, fillers, antifoaming agents, stabilizers, antioxidants, and fragrances.
  • the content of the other components is not particularly limited.
  • each component may be added in an amount of 0.1% relative to 100 parts by mass of the total composition for forming a passivation layer. It may be used at about 01 to 20 parts by mass. Other components may be used individually by 1 type, and may use 2 or more types together.
  • at least one kind of thixotropic agent By including at least one kind of thixotropic agent, the shape stability of the composition layer formed by applying the composition for forming a passivation layer on a semiconductor substrate was further improved, and the composition layer was formed as a passivation layer. The region can be selectively formed at a desired position in a desired shape.
  • thixotropic agents include fatty acid amides, polyalkylene glycol compounds, organic fillers, inorganic fillers, and the like.
  • polyalkylene glycol compound include compounds represented by the following general formula (VII).
  • R 10 and R 12 each independently represent a hydrogen atom or an alkyl group, and R 11 represents an alkylene group.
  • n is an arbitrary integer of 3 or more.
  • R 11 may be different even with the same in the presence of a plurality of (O-R 11).
  • fatty acid amides include compounds represented by the following general formulas (1), (2), (3) and (4).
  • R 13 CONH 2 (1) R 13 CONH—R 14 —NHCOR 13 (2) R 13 NHCO—R 14 —CONHR 13 (3) R 13 CONH—R 14 —N (R 15 ) 2 ... (4)
  • R 13 and R 15 each independently represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and R 14 represents 1 to 10 carbon atoms. Represents an alkylene group. R 13 and R 15 may be the same or different.
  • organic filler examples include acrylic resin, cellulose resin, and polystyrene resin.
  • Examples of the inorganic filler include particles of silicon dioxide, aluminum hydroxide, aluminum nitride, silicon nitride, aluminum oxide, zirconium oxide, silicon carbide, glass, and the like.
  • the volume average particle diameter of the organic filler or inorganic filler is preferably 0.01 ⁇ m to 50 ⁇ m.
  • the volume average particle diameter of the filler can be measured by a laser diffraction scattering method.
  • the composition for forming a passivation layer may contain a Bi oxide together with the compound of formula (I). Since the Bi oxide is an oxide formed by heat-treating (firing) the compound of formula (I), the passivation layer formed from the composition for forming a passivation layer containing the Bi oxide is excellent. A passivation effect is expected. Further, the composition for forming a passivation layer comprises at least one oxide selected from the group consisting of Nb, Ta, V, Y and Hf together with the specific aluminum compound or the compound of formula (III) (hereinafter referred to as “specific oxide”). May be included). Since the specific oxide is an oxide produced by heat-treating (firing) the specific aluminum compound or the compound of formula (III), the passivation layer formed from the composition for forming a passivation layer containing the specific oxide is: An excellent passivation effect is expected.
  • the viscosity of the composition for forming a passivation layer is not particularly limited, and can be appropriately selected depending on a method for applying the composition to a semiconductor substrate.
  • the viscosity of the passivation layer forming composition is preferably 0.01 Pa ⁇ s to 100,000 Pa ⁇ s.
  • the viscosity of the composition for forming a passivation layer is more preferably 0.1 Pa ⁇ s to 10,000 Pa ⁇ s.
  • the viscosity is measured at 25 ° C. and a shear rate of 1.0 s ⁇ 1 using a rotary shear viscometer.
  • the shear viscosity of the composition for forming a passivation layer is not particularly limited, and preferably has thixotropy.
  • shear viscosity eta 1 at a shear rate of 1.0 s -1, thixotropic index is calculated by dividing the shear viscosity eta 2 at a shear rate of 10s -1 ( ⁇ 1 / ⁇ 2 ) is, For example, it is preferably 1.05 to 100, more preferably 1.1 to 50.
  • the shear viscosity is measured at a temperature of 25 ° C. using a rotary shear viscometer equipped with a cone plate (diameter 50 mm, cone angle 1 °).
  • shear viscosity eta 1 at a shear rate of 1.0 s -1 the shear viscosity at a shear rate of 1000 s -1 eta
  • the thixo ratio ( ⁇ 1 / ⁇ 3 ) calculated by dividing by 3 is, for example, preferably from 1.05 to 100, and more preferably from 1.1 to 50.
  • the method for preparing the composition for forming a passivation layer can be produced by mixing a compound of formula (I) with water, an aluminum oxide precursor, a compound of formula (III), a liquid medium, a resin, etc., which are contained as necessary, by a commonly used mixing method. it can.
  • the composition for forming a passivation layer is prepared by dissolving the resin in a liquid medium and then mixing the compound with formula (I) and the like. It may be manufactured.
  • the aluminum oxide precursor When a specific aluminum compound is used as the aluminum oxide precursor, it may be prepared by mixing an aluminum alkoxide and a compound capable of forming a chelate with aluminum. At that time, a liquid medium may be appropriately used or heat treatment may be performed.
  • the components contained in the composition for forming a passivation layer, and the content of each component are determined by thermal analysis using a differential thermal-thermogravimetric measuring device (TG / DTA), nuclear magnetic resonance (NMR), infrared spectroscopy, etc. It can be confirmed by spectral analysis such as (IR), chromatographic analysis such as high performance liquid chromatography (HPLC), gel permeation chromatography (GPC) and the like.
  • TG / DTA differential thermal-thermogravimetric measuring device
  • NMR nuclear magnetic resonance
  • spectral analysis such as (IR)
  • HPLC high performance liquid chromatography
  • GPC gel permeation chromatography
  • the semiconductor substrate with a passivation layer of the present embodiment includes a semiconductor substrate and a passivation layer that is a heat treatment product of the composition for forming a passivation layer of the present embodiment provided on at least a part of at least one surface of the semiconductor substrate.
  • the semiconductor substrate with a passivation layer may further include other components as necessary.
  • the semiconductor substrate with a passivation layer exhibits an excellent passivation effect by having a passivation layer that is a heat-treated product of the composition for forming a passivation layer of the present embodiment.
  • the semiconductor substrate is not particularly limited, and can be appropriately selected from those usually used according to the purpose.
  • the semiconductor substrate for example, a substrate made of silicon, germanium, or the like, doped (diffused) with p-type impurities or n-type impurities can be used.
  • the semiconductor substrate is preferably a silicon substrate.
  • the semiconductor substrate may be a p-type semiconductor substrate or an n-type semiconductor substrate.
  • the surface on which the passivation layer is formed is a semiconductor substrate having a p-type layer.
  • the p-type layer on the semiconductor substrate is a p-type layer derived from the p-type semiconductor substrate
  • the p-type layer is formed on the n-type semiconductor substrate or the p-type semiconductor substrate as a p-type diffusion layer or a p + -type diffusion layer. It may be a thing.
  • the thickness of the semiconductor substrate is not particularly limited and can be appropriately selected depending on the purpose.
  • the thickness of the semiconductor substrate is preferably 50 ⁇ m to 1000 ⁇ m, and more preferably 75 ⁇ m to 750 ⁇ m.
  • the thickness of the passivation layer formed on the semiconductor substrate is not particularly limited and can be appropriately selected depending on the purpose.
  • the average thickness of the passivation layer is preferably 200 nm or less, more preferably 5 nm to 200 nm, still more preferably 10 nm to 190 nm, and particularly preferably 15 nm to 180 nm.
  • the average thickness of the formed passivation layer is calculated as an arithmetic average value by measuring the thickness at nine points by an ordinary method using an automatic ellipsometer (for example, MARY-102 manufactured by Fibrabo).
  • the semiconductor substrate with a passivation layer of the present embodiment can be applied to a solar cell element, a light emitting diode element, or the like.
  • a solar cell element excellent in power generation performance can be obtained by applying to a solar cell element.
  • the passivation layer is preferably provided on the light receiving surface side of the solar cell element.
  • the method for manufacturing a semiconductor substrate with a passivation layer of the present embodiment includes a step of forming the composition layer by applying the passivation layer forming composition of the present embodiment to at least a part of at least one surface of the semiconductor substrate; Forming a passivation layer by heat-treating (sintering) the composition layer.
  • the manufacturing method may further include other steps as necessary.
  • the semiconductor substrate to which the composition for forming a passivation layer is applied those described in the above-described semiconductor substrate with a passivation layer can be used.
  • the method for producing a semiconductor substrate with a passivation layer preferably further includes a step of applying an alkaline aqueous solution on the semiconductor substrate before the step of forming the composition layer. That is, it is preferable to wash the surface of the semiconductor substrate with an alkaline aqueous solution before applying the composition for forming a passivation layer on the semiconductor substrate. By washing with an alkaline aqueous solution, organic substances, particles, and the like present on the surface of the semiconductor substrate can be removed, and the passivation effect is further improved.
  • the semiconductor substrate can be immersed in a mixed solution of ammonia water and hydrogen peroxide solution and treated at 60 ° C. to 80 ° C. to remove organic substances and particles for cleaning.
  • the washing time is preferably, for example, 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes.
  • a known coating method or the like may be used. Specific examples include an immersion method, a printing method, an inkjet method, a dispenser method, a spin coating method, a brush coating method, a spray method, a doctor blade method, and a roll coating method. Among these, from the viewpoint of pattern formation and productivity, a printing method such as a screen printing method, an ink jet method, and the like are preferable, and a screen printing method is more preferable.
  • the application amount of the composition for forming a passivation layer can be appropriately selected according to the purpose.
  • the thickness of the passivation layer to be formed can be appropriately adjusted so as to be the above-described desired thickness.
  • a passivation layer is formed on a semiconductor substrate by heat-treating (baking) the composition layer formed by the composition for forming a passivation layer to form a heat-treated material layer (baked material layer) derived from the composition layer.
  • the heat treatment (firing) condition of the composition layer is a heat treated product (firing product) of the compound of formula (I) contained in the composition layer, the aluminum oxide precursor and the compound of formula (III) contained as necessary.
  • the heat treatment (firing) temperature is preferably 300 ° C.
  • the heat treatment (firing) time can be appropriately selected according to the heat treatment (firing) temperature and the like, and for example, it is preferably 30 seconds to 10 hours, and more preferably 1 minute to 5 hours.
  • a method for manufacturing a semiconductor substrate with a passivation layer is a method for forming a passivation layer after applying a passivation layer forming composition to a semiconductor substrate to form a composition layer and then forming a passivation layer by heat treatment (firing). You may further have the process of drying the composition layer which consists of a composition. By having the process of drying the composition layer, a passivation layer having a more uniform passivation effect can be formed.
  • the step of drying the composition layer removes at least a part of water that may be contained in the composition for forming a passivation layer and at least a part of a liquid medium that may be contained in the composition for forming a passivation layer.
  • the drying treatment is preferably a heat treatment at 30 ° C. to 600 ° C. for 5 seconds to 60 minutes, and more preferably a heat treatment at 40 ° C. to 450 ° C. for 30 seconds to 40 minutes.
  • the drying treatment may be performed under normal pressure or under reduced pressure.
  • the method for manufacturing a semiconductor substrate with a passivation layer includes forming the composition layer by applying the composition for forming a passivation layer, and then forming the passivation layer by heat treatment (firing). You may further have the process of degreasing a composition layer before a process. By having a step of degreasing the composition layer, a passivation layer having a more uniform passivation effect can be formed.
  • the step of degreasing the composition layer is not particularly limited as long as at least part of the resin that may be contained in the composition for forming a passivation layer can be removed.
  • the degreasing treatment is preferably a heat treatment at 30 ° C. to 600 ° C. for 5 seconds to 60 minutes, more preferably a heat treatment at 40 ° C. to 450 ° C. for 30 seconds to 40 minutes.
  • the degreasing treatment is preferably performed in the presence of oxygen, and more preferably performed in the air.
  • the solar cell element according to the present embodiment is provided on at least a part of a semiconductor substrate having a pn junction part in which a p-type layer and an n-type layer are pn-junction, and at least one surface of the semiconductor substrate.
  • a passivation layer which is a heat-treated product of the passivation layer forming composition, and an electrode disposed on at least one of the p-type layer and the n-type layer.
  • the solar cell element may further include other components as necessary.
  • the solar cell element of this embodiment is excellent in power generation performance by having the passivation layer formed from the composition for forming a passivation layer of this embodiment.
  • the semiconductor substrate to which the composition for forming a passivation layer is applied is not particularly limited, and can be appropriately selected from those usually used according to the purpose.
  • the semiconductor substrate used in the solar cell element those described in the section of the semiconductor substrate with a passivation layer can be used, and those that can be suitably used are also the same.
  • the thickness of the passivation layer formed on the semiconductor substrate can be appropriately selected according to the purpose.
  • the average thickness of the passivation layer is preferably 5 nm to 200 nm, more preferably 10 nm to 190 nm, and further preferably 15 nm to 180 nm.
  • the passivation layer of the present embodiment is formed on at least a part of at least one surface of a semiconductor substrate having a pn junction formed by pn junction of a p-type layer and an n-type layer. Applying a composition for forming a composition layer, heat-treating (firing) the composition layer to form a passivation layer, and on at least one of the p-type layer and the n-type layer And a step of disposing an electrode.
  • the manufacturing method of the solar cell element of this embodiment may further have other processes as needed.
  • a solar cell element having excellent power generation performance can be produced by a simple method.
  • an electrode can be manufactured by applying a paste for forming an electrode such as a silver paste or an aluminum paste to a desired region of a semiconductor substrate and performing a heat treatment (firing) as necessary.
  • the surface of the semiconductor substrate on which the passivation layer is provided may be a p-type layer or an n-type layer. Among these, from the viewpoint of power generation performance, the surface of the semiconductor substrate is preferably a p-type layer.
  • the details of the method for forming a passivation layer using the composition for forming a passivation layer are the same as the method for manufacturing a semiconductor substrate with a passivation layer described above, and the preferred embodiments are also the same.
  • the manufacturing method of the solar cell element of this embodiment will be described with reference to the drawings, but the present invention is not limited to this.
  • size of the member in each figure is notional, The relative relationship of the magnitude
  • symbol is attached
  • FIG. 1 is a cross-sectional view schematically showing an example of a method for producing a solar cell element having a passivation layer.
  • this process diagram does not limit the present invention at all.
  • the p-type semiconductor substrate 1 is washed with an alkaline aqueous solution to remove organic substances, particles and the like on the surface of the p-type semiconductor substrate 1. Thereby, the passivation effect improves more.
  • a cleaning method using an alkaline aqueous solution a method using generally known RCA cleaning and the like can be mentioned.
  • the surface of the p-type semiconductor substrate 1 is subjected to alkali etching or the like to form irregularities (also referred to as a texture structure) on the surface.
  • irregularities also referred to as a texture structure
  • reflection of sunlight can be suppressed on the light receiving surface side.
  • alkali etching an etching solution composed of NaOH and IPA (isopropyl alcohol) can be used.
  • an n + -type diffusion layer 2 is formed with a thickness on the order of submicrons, and p A pn junction is formed at the boundary with the mold bulk portion.
  • a method for diffusing phosphorus for example, a method of performing several tens of minutes at 800 ° C. to 1000 ° C. in a mixed gas atmosphere of phosphorus oxychloride (POCl 3 ), nitrogen, and oxygen can be cited.
  • phosphorus is diffused using a mixed gas, as shown in FIG. 1 (3), in addition to the light receiving surface (front surface), n + type is also applied to the back surface and side surfaces (not shown).
  • a diffusion layer 2 is formed.
  • a PSG (phosphosilicate glass) layer 3 is formed on the n + -type diffusion layer 2. Therefore, side etching is performed to remove the side PSG layer 3 and the n + -type diffusion layer 2.
  • the PSG layer 3 on the light receiving surface and the back surface is removed using an etching solution such as hydrofluoric acid. Further, as shown in FIG. 1 (5), the back surface is separately etched to remove the n + -type diffusion layer 2 on the back surface.
  • an antireflection film 4 made of silicon nitride or the like is provided on the n + -type diffusion layer 2 on the light-receiving surface by a plasma CVD (PECVD) method or the like with a thickness of about 90 nm.
  • PECVD plasma CVD
  • the back surface may be flattened using an aqueous alkali solution such as NaOH.
  • a passivation layer forming composition is applied to a part of the back surface by a screen printing method or the like, followed by heat treatment (baking) at a temperature of 300 ° C. to 900 ° C. after drying. Then, the passivation layer 5 is formed.
  • FIG. 5 an example of the formation pattern of the passivation layer in the back surface is shown as a schematic plan view.
  • FIG. 7 is an enlarged schematic plan view of a portion A in FIG.
  • FIG. 8 is an enlarged schematic plan view of a portion B in FIG.
  • the passivation layer 5 on the back surface is a dot-like pattern except for the portion where the back surface output extraction electrode 7 is formed in a later step. Formed with.
  • the pattern of the dot-shaped openings is defined by the dot diameter (L a ) and the dot interval (L b ), and is preferably arranged regularly.
  • the dot diameter (L a ) and the dot interval (L b ) can be arbitrarily set.
  • L a is 5 ⁇ m to 2 mm and L b is 10 ⁇ m to 3 mm. More preferably, L a is 10 ⁇ m to 1.5 mm and L b is 20 ⁇ m to 2.5 mm, and more preferably L a is 20 ⁇ m to 1.3 mm and L b is 30 ⁇ m to 2 mm.
  • the dot diameter (L a ) and the dot interval (L b ) are more regularly arranged in this dot-like opening pattern. For this reason, recombination of minority carriers is effectively suppressed, and the power generation efficiency of the solar cell element is improved.
  • FIG. 9 is an enlarged schematic plan view of a portion A in FIG.
  • FIG. 10 is an enlarged schematic plan view of a portion B in FIG.
  • the passivation layer 5 on the back surface is p-type in a line shape except for a portion where the back surface output extraction electrode 7 is formed in a later step.
  • the semiconductor substrate 1 is formed with an exposed pattern.
  • the pattern of the line openings is defined by the line width (L c ) and the line interval (L d ), and is preferably arranged regularly.
  • the line width (L c ) and the line interval (L d ) can be arbitrarily set.
  • L c is 1 ⁇ m to 300 ⁇ m and L d is 500 ⁇ m to 5000 ⁇ m. More preferably, L c is 10 ⁇ m to 200 ⁇ m, L d is 600 ⁇ m to 3000 ⁇ m, L c is 30 ⁇ m to 150 ⁇ m, and L d is 700 ⁇ m to 1500 ⁇ m.
  • the line width (L c ) and the line interval (L d ) are more regularly arranged in the pattern of the line-shaped openings. For this reason, recombination of minority carriers is effectively suppressed, and the power generation efficiency of the solar cell element is improved.
  • the passivation layer having a desired shape is formed by applying the passivation layer-forming composition to a portion (portion other than the opening) where the passivation layer is to be formed and heat-treating (firing).
  • the passivation layer forming composition is applied to the entire surface, and after the heat treatment (firing), the passivation layer in the opening can be selectively removed by laser, photolithography, or the like to form the opening.
  • the composition for forming a passivation layer can be selectively applied by previously masking a portion such as an opening where a composition for forming a passivation layer is not desired to be applied with a mask material.
  • FIG. 4 is a schematic plan view showing an example of the light receiving surface of the solar cell element.
  • the light receiving surface electrode includes a light receiving surface current collecting electrode 8 and a light receiving surface output extraction electrode 9.
  • the width of the light receiving surface current collecting electrode 8 is preferably 10 ⁇ m to 250 ⁇ m
  • the width of the light receiving surface output extraction electrode 9 is preferably 100 ⁇ m to 2 mm.
  • two light receiving surface output extraction electrodes 9 are provided.
  • the number of light receiving surface output extraction electrodes 9 may be three or more.
  • FIG. 11 is a schematic plan view showing an example of the back surface of the solar cell element.
  • the width of the back surface output extraction electrode 7 is not particularly limited, but the width of the back surface output extraction electrode 7 is preferably 100 ⁇ m to 10 mm from the viewpoint of the connectivity of the wiring material in the subsequent manufacturing process of the solar cell.
  • the glass particles contained in the silver electrode paste forming the light receiving surface electrode react with the antireflection film 4 (fire through),
  • the light-receiving surface electrode (light-receiving surface current collecting electrode 8, light-receiving surface output extraction electrode 9) and the n + -type diffusion layer 2 are electrically connected (ohmic contact).
  • aluminum in the aluminum electrode paste 6 is diffused into the p-type semiconductor substrate 1 by heat treatment (firing) from the portion where the dot-like or line-like passivation layer 5 is not formed, and thus p + A mold diffusion layer 10 is formed.
  • FIG. 2 is a cross-sectional view showing another example of a method for manufacturing a solar cell element having a passivation layer, and after the n + -type diffusion layer 2 on the back surface is removed by etching, A solar cell element can be manufactured in the same manner as in FIG. 1 except that the back surface is flattened.
  • a technique such as immersing the back surface of the semiconductor substrate in a mixed solution of nitric acid, hydrofluoric acid and acetic acid or a potassium hydroxide solution can be used.
  • FIG. 3 is a sectional view showing a process diagram showing another example of a method for producing a solar cell element having a passivation layer. This method is the same as the method shown in FIG. 1 until the step of forming the texture structure, the n + -type diffusion layer 2 and the antireflection film 4 on the p-type semiconductor substrate 1 (FIGS. 3 (19) to (24)). .
  • FIG. 6 shows a schematic plan view of another example of the formation pattern of the passivation layer on the back surface.
  • openings are arranged on the entire back surface, and dot-like openings are also arranged on the portion where the back surface output extraction electrode is formed in a later step.
  • boron or aluminum is diffused from the portion where the dot-like or line-like passivation layer 5 is not formed on the back surface, and the p + -type diffusion layer 10 is formed.
  • a method of treating at a temperature around 1000 ° C. in a gas containing boron trichloride (BCl 3 ) can be used.
  • the gas diffusion method is the same as in the case of using phosphorus oxychloride, the p + -type diffusion layer 10 is formed on the light-receiving surface, the back surface, and the side surface of the p-type semiconductor substrate 1. Therefore, it is necessary to take measures such as masking the portions other than the openings to prevent boron from diffusing into unnecessary portions of the p-type semiconductor substrate 1.
  • the p + -type diffusion layer 10 when aluminum is diffused when forming the p + -type diffusion layer 10, an aluminum paste is applied to the entire back surface or the opening, and this is heat-treated (fired) at 450 ° C. to 900 ° C.
  • the p + -type diffusion layer 10 can be formed by diffusing, and then a heat-treated product layer (baked product layer) made of an aluminum paste on the p + -type diffusion layer 10 can be etched with hydrochloric acid or the like.
  • the aluminum electrode 11 for backside current collection is formed by physically depositing aluminum on the entire backside.
  • a silver electrode paste containing glass particles is applied to the light receiving surface by screen printing or the like, and a silver electrode paste containing glass particles is applied to the back surface by a screen printing method or the like.
  • the silver electrode paste on the light receiving surface is applied in a pattern according to the shape of the light receiving surface electrode shown in FIG. 4, and the silver electrode paste on the back surface is applied in a pattern according to the shape of the back electrode shown in FIG.
  • the light receiving surface and the back surface are heat-treated (fired) at a temperature of about 450 ° C. to 900 ° C. in air, as shown in FIG.
  • a light receiving surface collecting electrode 8 and a light receiving surface output extraction electrode 9 are formed on the light receiving surface, and a back surface output extraction electrode 7 is formed on the back surface.
  • the light receiving surface electrode and the n + -type diffusion layer 2 are electrically connected, and on the back surface, the back surface collecting aluminum electrode 11 and the back surface output extraction electrode 7 formed by vapor deposition are electrically connected. Connected.
  • the passivation layer is formed after forming the back surface collecting aluminum electrode 6 or 11. 5 may be formed.
  • the passivation layer forming composition is applied to the side surface in addition to the back surface of the p-type semiconductor substrate 1, and this is subjected to heat treatment (
  • the passivation layer 5 may be further formed on the side surface (edge) of the p-type semiconductor substrate 1 by baking (not shown). Thereby, the solar cell element which is more excellent in power generation efficiency can be manufactured.
  • the passivation layer 5 may be formed by applying the composition for forming a passivation layer of the present embodiment only on the side surface, and heat-treating (firing) the surface without forming the passivation layer 5 on the back surface.
  • the composition for forming a passivation layer of the present embodiment is used in a place where there are many crystal defects such as side surfaces, the effect is particularly great.
  • FIGS. 1 to 3 show an example in which the p-type semiconductor substrate 1 is used as the semiconductor substrate. However, even when an n-type semiconductor substrate is used, a solar cell element having excellent conversion efficiency can be manufactured according to the above. .
  • the solar cell of the present embodiment includes at least one of the solar cell elements of the present embodiment, and is configured by arranging a wiring material on the electrode of the solar cell element. That is, the solar cell of this embodiment has the solar cell element and a wiring material disposed on the electrode of the solar cell element. Furthermore, the solar cell may be configured such that a plurality of solar cell elements may be connected via a wiring material as necessary, or may be configured to be sealed with a sealing material.
  • the wiring material and the sealing material are not particularly limited, and can be appropriately selected from those usually used in the technical field. There is no limitation on the size of the solar cell, for example, is preferably 0.5m 2 ⁇ 3m 2.
  • composition 1 for forming a passivation layer 8.8926 g of tris (2-ethylhexanoic acid) bismuth (Amax Co., Ltd., structural formula: Bi (OCOCHC 2 H 5 C 4 H 9 ) 3 , molecular weight: 638.6), aluminum ethyl acetoacetate diisopropylate (river Ken Fine Chemical Co., Ltd., trade name: ALCH) 3.8224 g, Terpineol (Nippon Terpene Chemical Co., Ltd., sometimes abbreviated as TPO) 25.7915 g, Isobornyl cyclohexanol (Nippon Terpene Chemical Co., Ltd., MTPH) 66.1969 g (which may be abbreviated) was mixed and kneaded for 5 minutes, and then 1.2349 g of pure water was added and further kneaded for 5 minutes to prepare a composition 1 for forming a passivation layer
  • the prepared composition 1 for forming a passivation layer was printed on the entire surface using a screen printing method on a single crystal p-type silicon substrate (156 mm square, thickness 180 ⁇ m, hereinafter referred to as a silicon substrate) having a mirror surface. Thereafter, the silicon substrate provided with the passivation layer forming composition 1 is heated at 450 ° C. for 5 minutes using a walking beam furnace (Noritake Co., Ltd., a baking furnace for solar cell heat treatment apparatus R & D) to evaporate the liquid medium. And dried.
  • a walking beam furnace Neoritake Co., Ltd., a baking furnace for solar cell heat treatment apparatus R & D
  • the silicon substrate was heat-treated (fired) at a temperature of 750 ° C. for 10 minutes, and then allowed to cool at room temperature (25 ° C.).
  • the film formation state of the evaluation substrate obtained above was evaluated.
  • the evaluation substrate was randomly observed at 10 magnifications using an optical microscope (Olympus Corporation, MX51) at a magnification of 50 times. At this time, a case where there was no portion recognized as a crack or a crack was determined as good (A), and a case where one or more cracks or cracks were observed was determined as a failure (B).
  • the film formation state of the evaluation substrate obtained above was good.
  • the fixed charge density of the passivation layer formed on the evaluation substrate was evaluated.
  • a circular Al electrode of about 0.00025 cm 2 was deposited on the surface of the evaluation substrate on which the passivation layer was formed.
  • a prober was applied to the deposited Al electrode, and the fixed charge density was calculated by the CV method.
  • the fixed charge density of the passivation layer was ⁇ 2.1E + 12 ( ⁇ 2.1 ⁇ 10 12 ) cm ⁇ 2 .
  • Example 2 In Example 1, the blending amount was changed. Specifically, the content of each component is 10.7815 g of tris (2-ethylhexanoic acid) bismuth, 1.3015 g of ALCH, 23.8978 g of TPO, 62.3181 g of MTPH, and 0.7933 g of pure water.
  • the composition 2 for forming a passivation layer was prepared in the same manner as in Example 1 except that the above was changed. Thereafter, in the same manner as in Example 1, the film formation state of the passivation layer was evaluated and the fixed charge density was measured.
  • Example 3 In Example 1, the blending amount and materials were changed. Specifically, 8.0646 g of tris (2-ethylhexanoic acid) bismuth, 1.1439 g of ALCH, niobium ethoxide (Hokuko Chemical Co., Ltd., structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318 .2) is 1.3872 g, TPO is 22.5454 g, MTPH is 60.3796 g, and pure water is 1.0264 g. A composition 3 for forming a passivation layer is prepared in the same manner as in Example 1. did. Thereafter, in the same manner as in Example 1, the film formation state of the passivation layer was evaluated and the fixed charge density was measured.
  • Example 4 In Example 1, the blending amount and materials were changed. Specifically, 8.687 g of tris (2-ethylhexanoic acid) bismuth, 3.7254 g of ALCH, and a silicate agent (Tama Chemical Industry Co., Ltd., trade names: silicate 40, sometimes abbreviated as Si40) are 0.
  • a composition 4 for forming a passivation layer was prepared in the same manner as in Example 1 except that 3216 g, TPO 24.8716 g, MTPH 65.1844 g and pure water 1.2453 g were changed. Thereafter, in the same manner as in Example 1, the film formation state of the passivation layer was evaluated and the fixed charge density was measured.
  • Example 1 ⁇ Comparative Example 1>
  • the blending amount and materials were changed. Specifically, the same procedure as in Example 1 was performed except that 9.0168 g of bismuth oxide, 3.9165 g of aluminum oxide, 25.8568 g of TPO, 66.8321 g of MTPH, and 1.27664 g of pure water were changed. Thus, a passivation layer forming composition C1 was prepared. That is, in Comparative Example 1, the compound represented by the general formula (I) was not used. Thereafter, in the same manner as in Example 1, the film formation state of the passivation layer was evaluated and the fixed charge density was measured.
  • Example 1 In the preparation of the composition for forming a passivation layer in Example 1, the compound represented by the general formula (I) was not used. Specifically, the content of each component was the same as in Example 1 except that ALCH was changed to 11.6916 g, TPO was changed to 22.9814 g, MTPH was changed to 62.1949 g, and pure water was changed to 1.5219 g. A composition R1 for forming a passivation layer was prepared. Thereafter, in the same manner as in Example 1, the film formation state of the passivation layer was evaluated and the fixed charge density was measured.
  • ALCH was changed to 11.6916 g
  • TPO was changed to 22.9814 g
  • MTPH was changed to 62.1949 g
  • pure water was changed to 1.5219 g.
  • a composition R1 for forming a passivation layer was prepared. Thereafter, in the same manner as in Example 1, the film formation state of the passivation layer was evaluated and the fixed charge density was measured.
  • Table 1 shows the blending ratio, film formation state, and fixed charge density evaluation results for the compositions for forming a passivation layer implemented in Examples 1 to 4, Comparative Example 1, and Reference Example 1. It was found that the composition for forming a passivation layer produced in Examples 1 to 4 has a good film formation state and can form a passivation layer that expresses a large negative fixed charge of ⁇ 1E + 12 cm ⁇ 2 or more. It was.
  • 1 p-type semiconductor substrate
  • 2 n + -type diffusion layer
  • 3 PSG (phosphorus silicate glass) layer
  • 4 antireflection film
  • 5 passivation layer
  • 6 aluminum electrode paste, or heat-treated (fired)
  • 7 Back surface output extraction electrode paste, or back surface output extraction electrode obtained by heat treatment (baking)
  • 8 Light receiving surface current collection electrode paste, or light receiving surface current collection obtained by heat treatment (firing) Electrode
  • 9 Light receiving surface output extraction electrode paste, or light receiving surface output extraction electrode obtained by heat treatment (baking)
  • 10 p + type diffusion layer
  • 11 Aluminum electrode for backside current collection.

Landscapes

  • Photovoltaic Devices (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

L'invention porte sur une composition pour la formation d'une couche de passivation qui comprend le composé exprimé dans la formule générale (I). Bi (OR 1) m (I) [où R 1 représente un groupe alkyle indépendant, un groupe aryle ou un groupe acyle, et m représente 3 ou 5]
PCT/JP2016/086388 2016-06-28 2016-12-07 Composition pour formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de fabrication de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire Ceased WO2018003142A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016128085 2016-06-28
JP2016-128085 2016-06-28

Publications (1)

Publication Number Publication Date
WO2018003142A1 true WO2018003142A1 (fr) 2018-01-04

Family

ID=60786836

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/086388 Ceased WO2018003142A1 (fr) 2016-06-28 2016-12-07 Composition pour formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de fabrication de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire

Country Status (2)

Country Link
TW (1) TW201808976A (fr)
WO (1) WO2018003142A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015067475A (ja) * 2013-09-27 2015-04-13 国立大学法人北陸先端科学技術大学院大学 酸化物誘電体及びその製造方法、酸化物誘電体の前駆体、並びに固体電子装置及びその製造方法
JP2015135919A (ja) * 2014-01-17 2015-07-27 日立化成株式会社 パッシベーション層付半導体基板、パッシベーション層形成用塗布型材料及び太陽電池素子
WO2016002901A1 (fr) * 2014-07-04 2016-01-07 日立化成株式会社 Composition de formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de production de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015067475A (ja) * 2013-09-27 2015-04-13 国立大学法人北陸先端科学技術大学院大学 酸化物誘電体及びその製造方法、酸化物誘電体の前駆体、並びに固体電子装置及びその製造方法
JP2015135919A (ja) * 2014-01-17 2015-07-27 日立化成株式会社 パッシベーション層付半導体基板、パッシベーション層形成用塗布型材料及び太陽電池素子
WO2016002901A1 (fr) * 2014-07-04 2016-01-07 日立化成株式会社 Composition de formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de production de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire

Also Published As

Publication number Publication date
TW201808976A (zh) 2018-03-16

Similar Documents

Publication Publication Date Title
WO2014014110A9 (fr) Composition servant à former une couche de passivation, substrat semi-conducteur comprenant une couche de passivation, procédé de production d'un substrat semi-conducteur comprenant une couche de passivation, élément de cellule solaire, procédé de production d'un élément de cellule solaire, et cellule solaire
JP2015135858A (ja) パッシベーション膜付半導体基板及びその製造方法、並びにそれを用いた太陽電池素子及びその製造方法
WO2014014108A1 (fr) Composition formant une couche de passivation, substrat semi-conducteur ayant une couche de passivation, procédé de fabrication d'un substrat semi-conducteur ayant une couche de passivation, élément de cellule solaire, procédé de fabrication d'un élément de cellule solaire, et cellule solaire
CN104040701B (zh) 带钝化膜的半导体基板及其制造方法、以及太阳能电池元件及其制造方法
JP6330661B2 (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板及びその製造方法、並びに太陽電池素子及びその製造方法
TWI680979B (zh) 鈍化層形成用組成物、帶鈍化層的半導體基板及其製造方法、太陽電池元件及其製造方法以及太陽電池
JP2015115488A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法及び太陽電池
WO2014010744A1 (fr) Composition destinée à la formation d'une couche de passivation, substrat semi-conducteur doté d'une couche de passivation, procédé de fabrication d'un substrat semi-conducteur doté d'une couche de passivation, élément de cellule solaire, procédé de fabrication d'un élément de cellule solaire et cellule solaire
JP6424422B2 (ja) パッシベーション層付半導体基板の製造方法、パッシベーション層付半導体基板、太陽電池素子の製造方法及び太陽電池素子
JP2018174270A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法、及び太陽電池
JP2018006425A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法、及び太陽電池
JP2017188537A (ja) 太陽電池素子及びその製造方法並びに太陽電池
JP2017188536A (ja) 太陽電池素子及び太陽電池
JP2018006429A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板及びその製造方法、太陽電池素子及びその製造方法並びに太陽電池
WO2018003142A1 (fr) Composition pour formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de fabrication de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire
JP2019175951A (ja) パッシベーション層付半導体基板及びその製造方法、太陽電池素子及びその製造方法、並びに太陽電池
JP2018006431A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法、及び太陽電池
JP2018174268A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法、及び太陽電池
JP2018006424A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法、及び太陽電池
JP2018174269A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法、及び太陽電池
JP2017045834A (ja) 太陽電池用パッシベーション膜の製造方法
JP2018006426A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法、及び太陽電池
WO2018003141A1 (fr) Composition de formation de couche de passivation, substrat semi-conducteur à couche de passivation, procédé de fabrication de substrat semi-conducteur à couche de passivation, élément de cellule solaire, procédé de fabrication d'élément de cellule solaire, et cellule solaire
JP2018006428A (ja) パッシベーション層形成用組成物、パッシベーション層付半導体基板及びその製造方法、太陽電池素子及びその製造方法並びに太陽電池
JP2019175950A (ja) パッシベーション層付半導体基板、太陽電池素子、及び太陽電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16907374

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16907374

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP