US20070186970A1 - Solar cell and method of fabricating the same - Google Patents
Solar cell and method of fabricating the same Download PDFInfo
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- US20070186970A1 US20070186970A1 US10/556,063 US55606304A US2007186970A1 US 20070186970 A1 US20070186970 A1 US 20070186970A1 US 55606304 A US55606304 A US 55606304A US 2007186970 A1 US2007186970 A1 US 2007186970A1
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- solar cell
- insulating film
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- cell substrate
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Classifications
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- 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
- H10F10/00—Individual photovoltaic cells, e.g. solar cells
-
- 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
- H10F10/00—Individual photovoltaic cells, e.g. solar cells
- H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
- H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
- H10F10/146—Back-junction photovoltaic cells, e.g. having interdigitated base-emitter regions on the back side
-
- 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
- H10F10/00—Individual photovoltaic cells, e.g. solar cells
- H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
- H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
-
- 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
- H10F71/00—Manufacture or treatment of devices covered by this subclass
-
- 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
- H10F71/00—Manufacture or treatment of devices covered by this subclass
- H10F71/121—The active layers comprising only Group IV materials
-
- 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
- H10F71/00—Manufacture or treatment of devices covered by this subclass
- H10F71/129—Passivating
-
- 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
- H10F77/306—Coatings for devices having potential barriers
- H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- 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
- This invention relates to a solar cell capable of directly converting light energy to electric energy, and a method of fabricating the same.
- a solar cell is a semiconductor element capable of converting light energy into electric power, known types of which include p-n junction type, PIN type and Schottky type, among which the p-n junction type is widely used. It is also possible to roughly classify the solar cell into three types, based on materials composing the substrate, such as silicon crystal-base solar cell, amorphous-silicon-base solar cell and compound-semiconductor-base solar cell. The silicon-crystal-base solar cell is further classified into single-crystal-base solar cell and polycrystal-base solar cell. The silicon-crystal-base solar cell is most disseminated, because silicon crystal substrate for producing the solar cell can be fabricated in a relatively easy manner.
- Output characteristics of the above-described solar cell can generally be assessed by measuring an output current-voltage curve using a solar simulator.
- Point Pm on the curve, giving a maximum product Ip ⁇ Vp of output current Ip and output voltage Vp is referred to as maximum output Pm, and a value obtained by dividing Pm by the total light energy incident on the solar cell (S ⁇ I: S is element area and I is intensity of irradiated light): ⁇ Pm/ ( S ⁇ I ) ⁇ 100(%) (1) is defined as conversion efficiency ⁇ of the solar cell.
- Known high-efficiency solar cells therefore improve the conversion efficiency ⁇ by protecting the light receiving surface and the back surface of the semiconductor substrate, excluding contact portions with the electrodes, with an insulating film, so as to suppress recombination of the carriers at the interface between the semiconductor substrate and the individual insulating films (so-called surface passivation effect).
- Silicon oxide film has long been used as this sort of insulating film, but the refractive index of which is as small as 1.4 or around, and causes a slightly large reflection loss when used on the light-receiving-surface-side. For this reason, in recent years, there has been an increasing trend in using silicon nitride, having a larger refractive index, and being excellent not only in the passivation effect but also in anti-reflection effect.
- the silicon nitride film has conventionally been formed by the CVD (chemical vapor deposition) process such as thermal CVD, plasma CVD, photo CVD and so forth. Among these, most generally disseminated is plasma CVD.
- FIG. 3 schematically shows a batch-type, parallel-plate plasma CVD apparatus, generally called a direct plasma CVD.
- the apparatus comprises a reaction vessel 1 equipped with an evacuation device 11 , substrate holders 81 placing solar cell substrates 20 at predetermined positions in the reaction vessel 1 , film forming gas introducing ducts 31 , 32 introducing predetermined film-forming gases, which are reactive gases, into the reaction vessel 1 , a high-frequency power source 82 generating plasma by energizing the introduced gas, and a resistance-heating heater 90 keeping a deposition atmosphere at a constant temperature.
- predetermined film-forming gases are introduced into the reaction vessel 1 at predetermined flow rates through the film forming gas introducing ducts 31 , 32 , and the high-frequency power source 82 is then operated to set a high-frequency electric field.
- the high-frequency power source 82 is then operated to set a high-frequency electric field.
- silane is introduced through the film forming gas introducing duct 31 , and ammonia is introduced through the film forming gas introducing duct 32 , as the film-forming gases, the both are mixed and then supplied to the reaction vessel 1 , so as to produce the silicon nitride film making use of decomposition reaction and so forth of silane in the plasma.
- the plasma CVD is widely applied to processes of fabricating solar cells because it can ensure a relatively high deposition rate even under a substrate temperature of relatively as low as 400° C.
- the process raises a problem in that high-energy charged particles produced in the plasma are highly causative of damages of the deposited film or the surface of the substrates (so-called plasma damage), so that the obtained silicon nitride film tends to have a large interface state density, and consequently results in only a poor passivation effect. This is also highly affective to various characteristics of the solar cell.
- FIG. 4 schematically shows an exemplary apparatus used therefor. Unlike the conventional plasma CVD process, this method is characterized in that the surface of the substrate to be treated is placed apart from a plasma region (plasma zone) so as to make use of radical species in a separated manner, allowing this method to be referred to as “remote plasma CVD”, hereinafter.
- plasma CVD electrospray cyclotron resonance
- a predetermined film-forming gas is introduced into a pre-chamber 101 at a predetermined flow rate through a film forming gas introducing duct 31 , and microwaves, in place of high-frequency electric field, are applied to the pre-chamber 101 using a microwave generator 102 .
- the microwaves raise the plasma of the film-forming gas, used also as a carrier gas, and generates reactive species.
- the reactive species flow into the process chamber 1 , and causes chemical reactions with the other film-forming gas supplied through the film forming gas introducing duct 32 , thereby an insulating film is formed on the surface of the substrate 20 .
- ammonia as a film-forming gas used also as a carrier gas, is introduced through the film forming gas introducing duct 31 , and silane is introduced through the introducing duct 32 , the both are mixed, so as to produce the silicon nitride film making use of ammonia decomposition reaction and so forth in the plasma.
- the remote plasma CVD is partially successful in reducing the plasma damage.
- thus-obtained silicon nitride film contains hydrogen atoms to a maximum of 40 at %, and is causative of time-dependent degradation in the passivation effect under sustained irradiation of light, such as sunray, containing a large energy of ultraviolet radiation.
- the conventional silicon nitride film formed by the plasma CVD process has also been shifted in the film composition thereof from the stoichiometric composition towards the silicon-excessive side to a considerably large degree, in order to obtain so-called field effect passivation.
- a large shift in the film composition towards the silicon-excessive side causes effluence of electrons produced by anion deficiency towards the semiconductor substrate so as to produce positive fixed charge on the cation side, and this results in band bending. This induces formation of an inversion layer in which electrons are excessive in the vicinity of the contact interface on the semiconductor substrate side, with which the passivation effect can be enhanced.
- an inversion layer 112 formed in the p-type substrate 111 in the vicinity of an electrode 64 as shown in FIG. 5 tends to cause short-circuiting within an electrode surface, and this consequently results in a decrease in the generated current.
- the surface of the emitter layer is too high in the dopant concentration, so that the band bending can hardly occur only with an amount of fixed charge as much as residing in the silicon nitride film, and the field effect passivation is far from being expected. It can therefore be said that suppression of the plasma damage and consequent suppression of the interface states in the emitter layer hold the key for a desirable passivation.
- Such desirable passivation cannot be obtained anyhow, because it is difficult to suppress damage by the general plasma CVD.
- a solar cell according to the first aspect of this invention is characterized by comprising a semiconductor solar cell substrate having a light receiving surface formed on a first major surface thereof, and generating photovoltaic power based on the light irradiated on the light receiving surface, wherein the light receiving surface of the semiconductor solar cell substrate is covered with a light-receiving-surface-side insulating film provided as an inorganic insulating film composed of an inorganic insulating material having a cationic component thereof principally comprising silicon, and the light-receiving-surface-side insulating film is configured as a low-hydrogen-content inorganic insulating film having a hydrogen content of less than 10 at %.
- a cationic component thereof principally comprising silicon in this patent specification means that 50% or more (preferably 80% or more) of the cationic component of the inorganic insulating material is silicon. Any cation other than silicon may be contained so far as the effects of this invention described below can be achieved, without excessively impairing the insulating property of the material. For example, it is possible to introduce alkali metal ions having a large ionic radius, such as cesium ions, so as to increase the fixed charge in the film, to thereby allow them to contribute to the field effect passivation.
- the light-receiving-surface-side insulating film is configured using a silicon-base insulating film having a large dielectric constant and being capable of providing a desirable passivation effect, and is also configured as a low-hydrogen-content inorganic insulating film, having a hydrogen content of less than 10 at %, so that the durability of the light-receiving-surface-side insulating film against ultraviolet radiation can be improved to a large degree.
- the passivation effect of the insulating film is less likely to cause time-dependent degradation even if the solar cell is used under an environment in which a light having a large energy content of ultraviolet radiation such as a sunray and a fluorescent lamp is irradiated for a long duration of time, and the conversion efficiency ⁇ can be maintained at a desirable value for a long period.
- the silicon-base insulating film can be formed by the CVD process.
- a method of fabricating a solar cell according to the first aspect of this invention is such as fabricating a solar cell which comprises a semiconductor solar cell substrate having a light receiving surface formed on a first major surface thereof, and also having a p-n junction generating photovoltaic power based on the light irradiated on the light receiving surface, the light receiving surface of the semiconductor solar cell substrate being covered with a light-receiving-surface-side insulating film composed of an inorganic insulating film having a cationic component thereof principally comprising silicon, wherein the light-receiving-surface-side insulating film is formed as a low-hydrogen-content inorganic insulating film having a hydrogen content of less than 10 at %, by the catalytic CVD process in which a heat catalyst is placed together with the semiconductor solar cell substrate in a reaction vessel; and a film-forming gas, which comprises a silicon source gas and an anion source gas producing an
- a mixed gas of silane (SiH 4 ) and ammonia (NH 3 ) is used and introduced as the film-forming gas.
- the heat catalyst may be any metal (or alloy) having a catalytic activity of a certain level or above, and can be configured typically by tungsten, molybdenum, tantalum, titanium or vanadium.
- the catalytic CVD process adopted as described in the above makes it possible to deposit an insulating film with a less amount of interfacial defect while keeping composition thereof constant, and further makes it possible to obtain a silicon-base insulating film highly excellent in the passivation effect.
- the catalytic CVD process is enhanced in the reaction efficiency by virtue of a catalyst, and allows deposition of a high-quality insulating film without excessively diluting the film-forming gas with a carrier gas such as hydrogen. It is also possible to suppress the residual content of hydrogen derived from the film-forming gas.
- the composition is selected so as to suppress generation of dangling bonds of silicon atoms, which can readily bind with hydrogen atoms (for an exemplary case of silicon nitride, a composition such as being not so departing in the silicon-excessive side from the stoichiometric ratio).
- the catalytic CVD process can readily produce a silicon-base insulating film having a hydrogen content of less than 10 at %, while still relying upon CVD process.
- it is more effective to adopt a method of supplying the film-forming gas into the reaction vessel without diluting it with hydrogen.
- the semiconductor solar cell substrate can be configured, similarly to that of other known solar cells, using single-crystal silicon, polysilicon, gallium arsenide, germanium or other composite materials.
- single-crystal silicon it is preferable to use single-crystal silicon as the semiconductor solar cell substrate (the same will apply also to second and third aspects of this invention described later).
- a second major surface of the semiconductor solar cell substrate may be covered with a back-side insulating film provided as an inorganic insulating film composed of an inorganic insulating material having a cationic component thereof principally comprising silicon, a back electrode may be provided so as to cover the back-side insulating film and so as to contact with the back surface of the semiconductor solar cell substrate through conductive portions penetrating the back-side insulating film, and the back-side insulating film may be configured as a low-hydrogen-content inorganic insulating film having a hydrogen content of less than 10 at %.
- the ultraviolet resistant characteristics and, consequently, time-dependent stability of the passivation effect can be improved by configuring also the back-side insulating film as a low-hydrogen-content insulating film.
- the hydrogen content of the low-hydrogen-content inorganic insulating film exceeding 10 at % tends to degrade the passivation effect due to ultraviolet irradiation, and prevents the object of this invention from being attained.
- the hydrogen content of the low-hydrogen-content inorganic insulating film suppressed beyond 1 at % results in saturation of the ultraviolet radiation resistant characteristics, and may undesirably raise the cost due to complication of the process and so forth. Therefore the hydrogen content of the low-hydrogen-content inorganic insulating film is preferably adjusted within a range from 1 at % to 10 at %, both ends inclusive, and more preferably from 1 at % to 5 at %.
- the silicon-base inorganic insulating material composing the light-receiving-surface-side insulating film or the back-side insulating film can specifically be composed of any one of silicon nitrides, silicon oxides and silicon oxynitrides.
- silicon nitride excellent in the passivation effect, can effectively be used for this invention.
- Silicon nitride is also advantageous in having a large refractive index, and therefore can be used also as an anti-reflection film if it is applied to the light-receiving-surface-side insulating film (the same will apply also to the second and third aspects of this invention described later).
- the light-receiving-surface-side insulating film is preferably configured as a low-hydrogen-content inorganic insulating film composed of silicon nitride having a refractive index of 2 to 2.5, both ends inclusive.
- the refractive index smaller than 2 results in only a non-distinctive, anti-reflection effect, whereas exceeding 2.5 induces optical absorption of the light-receiving-surface-side insulating film in the wavelength range contributive to conversion of the incident light into current, and thereby lowers the conversion efficiency.
- the light-receiving-surface-side insulating film is adjusted to have a refractive index of 2 to 2.1, both ends inclusive.
- the refractive index of the silicon nitride film is closely related to its silicon/nitrogen atomic ratio (Si/N atomic ratio), showing a tendency of increasing the refractive index as the atomic ratio of silicon increases.
- Si/N atomic ratio silicon/nitrogen atomic ratio
- the present inventors found through investigations that it was preferable to adjust the Si/N atomic ratio within a range from 0.80 to 1.80.
- the inorganic film to be obtained is the above-described silicon nitride film
- the silicon source gas is silane (defined as generally referring to silicon hydrides: specifically includes monosilane and disilane) and the nitrogen source is ammonia
- the Si/N atomic ratio of the resultant silicon nitride film can be adjusted by ratio of flow rates of silane and ammonia supplied to the reaction vessel.
- the Si/N atomic ratio of the silicon nitride film is adjustable also by pressure of a mixed gas of the silicon source gas and the nitrogen source gas. More specifically, under a constant ratio of mixing of the silicon source gas and the nitrogen source gas, the Si/N atomic ratio of the silicon nitride film is adjustable towards the nitrogen-rich direction by increasing the gas pressure, and towards the silicon-rich direction by decreasing the gas pressure.
- the back-side insulating film may be a silicon nitride film formed, so as to adjust the Si/N atomic ratio thereof to 0.80 to 1.80, both ends inclusive, by the catalytic CVD process in which a heat catalyst is placed together with the semiconductor solar cell substrate in a reaction vessel; and a film-forming gas, which is comprised of a silicon source gas and a nitrogen source gas, is supplied to the surface of the semiconductor solar cell substrate while making the film-forming gas into contact with the heat catalyst, so as to deposit silicon nitride produced based on chemical reactions of the film-forming gas on the surface of the semiconductor solar cell substrate.
- a film-forming gas which is comprised of a silicon source gas and a nitrogen source gas
- a second aspect of the solar cell of this invention is characterized in comprising a semiconductor solar cell substrate having a light receiving surface formed on the first major surface thereof, and generating photovoltaic power based on the light irradiated on the light receiving surface, wherein a second major surface of the semiconductor solar cell substrate is covered with a back-side insulating film provided as an inorganic insulating film composed of silicon nitride, and a back electrode is provided so as to cover the back-side insulating film and so as to contact with the back surface of the semiconductor solar cell substrate through conductive portions penetrating the back-side insulating film, and
- the silicon nitride film composing the back-side insulating film is formed so as to adjust the Si/N atomic ratio thereof to 0.80 to 1.80, both ends inclusive, by the catalytic CVD process in which a heat catalyst is placed together with the semiconductor solar cell substrate in a reaction vessel; and a film-forming gas, which comprises a silicon source gas and a nitrogen source gas, is supplied to the surface of the semiconductor solar cell substrate while making the film-forming gas into contact with the heat catalyst, so as to deposit silicon nitride produced based on chemical reactions of the film-forming gas on the surface of the semiconductor solar cell substrate.
- a film-forming gas which comprises a silicon source gas and a nitrogen source gas
- a second aspect of the method of fabricating a solar cell of this invention is characterized by a method of fabricating a solar cell which comprises a solar cell comprising a semiconductor solar cell substrate having a light receiving surface formed on the first major surface thereof, and generating photovoltaic power based on the light irradiated on the light receiving surface, wherein a second major surface of the semiconductor solar cell substrate is covered with a back-side insulating film provided as an inorganic insulating film composed of silicon nitride, and a back electrode is provided so as to cover the back-side insulating film so as to contact with the back surface of the semiconductor solar cell substrate through conductive portions penetrating the back-side insulating film, and
- the silicon nitride film composing the back-side insulating film is formed by the catalytic CVD process in which a heat catalyst is placed together with the semiconductor solar cell substrate in a reaction vessel; and a film-forming gas, which comprises a silicon source gas and a nitrogen source gas, is supplied to the surface of the semiconductor solar cell substrate while making the film-forming gas into contact with the heat catalyst, so as to deposit silicon nitride produced based on chemical reactions of the film-forming gas on the surface of the semiconductor solar cell substrate, while regulating the ratio of mixing of the silicon source gas and the nitrogen source gas so as to adjust the Si/N atomic ratio to 0.80 to 1.80, both ends inclusive.
- Silane and ammonia can be used as the silicon source gas and the nitrogen source gas, as described above.
- the film of this sort having a composition close to the stoichiometric ratio, has a less amount of fixed charge ascribable to electrons caused by excessive silicon, and is less causative of band bending even if it is bonded to the back surface of the semiconductor solar cell substrate.
- An inversion layer formed on the substrate side can therefore be thinned, and this makes short-circuiting within the electrode surface of the back electrode, as shown in FIG. 5 , very unlikely to occur.
- the film is less causative of defects like dangling bonds possibly providing sites for surface recombination, and is therefore successful in obtaining a desirable passivation effect.
- Adjustment of the Si/N atomic ratio of the silicon nitride film within a range from 0.80 to 1.80 also makes it possible to reduce the hydrogen content, so that, similarly to the case of the light-receiving-surface-side insulating film, the ultraviolet resistant characteristics and, consequently, time-dependent stability of the passivation effect of the back-side insulating film can be improved, in a bifacial solar cell having the back electrode not covering the entire surface of the back-side insulating film and allowing also the incident light on the back surface to contribute to power generation.
- the low-defect, high-quality silicon nitride film having a composition expressed by a Si/N atomic ratio of 0.80 to 1.80, close to the stoichiometric ratio, can be obtained by the catalytic CVD process as described above, a desirable passivation effect can be obtained without relying upon the field-effect passivation effect which is contributed by polarity of the inversion layer, and consequently the silicon nitride film can be used both as an insulating film on the light-receiving surface side and as an insulating film on the back side, unlike the silicon-excessive silicon nitride film, and can exhibit the specific effects for both sides.
- the inorganic insulating film can be deposited by the catalytic CVD process on the surface of the semiconductor solar cell substrate after being surface-treated by introducing a surface treatment gas into the reaction vessel, and by supplying the surface treatment gas to the surface of the semiconductor solar cell substrate so as to effect the surface treatment, while making the film-forming gas come into contact with the heat catalyst.
- the general plasma CVD process results in formation of a trace amount of an oxygen-containing transition layer between the substrate and the insulating film, which is, for example, a silicon oxynitride film for the case of silicon nitride film, causative of formation of interfacial defects, whereas the above-described surface treatment can effectively remove the transition layer, can more effectively suppress the formation of interfacial defects, and can more effectively prevent the conversion efficiency of the solar cell from degrading due to surface recombination.
- the semiconductor solar cell substrate is a silicon substrate and the inorganic insulating film is a silicon nitride film
- ammonia gas as the surface treatment gas.
- the inorganic insulating film may be deposited by the catalytic CVD process on the surface of the semiconductor solar cell substrate, and may be post-treated by introducing a post-treatment gas into the reaction vessel, and by supplying the post-treatment gas to the surface of the inorganic insulating film, while keeping the post-treatment gas in contact with the heat catalyst.
- a third aspect of the solar cell according to this invention is characterized in comprising a semiconductor solar cell substrate having a light receiving surface formed on the first major surface thereof, and generating photovoltaic power based on the light irradiated on the light receiving surface, wherein a second major surface of the semiconductor solar cell substrate is covered with a back-side insulating film composed of an inorganic insulating film having a cationic component thereof principally comprising silicon, and a back electrode is provided so as to cover the back-side insulating film and so as to contact with the back surface of the semiconductor solar cell substrate through conductive portions penetrating the back-side insulating film, and
- the inorganic insulating film is such as being deposited and formed by the catalytic CVD process in which a heat catalyst is placed together with the semiconductor solar cell substrate in a reaction vessel; and a film-forming gas, which comprises a silicon source gas and an anion source gas producing an anionic component capable of binding with silicon in an inorganic material to be obtained, is supplied to the surface of the semiconductor solar cell substrate while making the film-forming gas into contact with the heat catalyst, so as to deposit an inorganic insulating material produced based on chemical reactions of the film-forming gas on the surface of the semiconductor solar cell substrate; and such as being post-treated by introducing a post-treatment gas into the reaction vessel, and by supplying the post-treatment gas to the surface of the inorganic insulating film, while keeping the post-treatment gas in contact with the heat catalyst.
- a film-forming gas which comprises a silicon source gas and an anion source gas producing an anionic component capable of binding with silicon in an inorganic material to be obtained
- a third aspect of the method of fabricating a solar cell according to this invention is characterized by a method of fabricating a solar cell which comprises a semiconductor solar cell substrate having a light receiving surface formed on a first major surface thereof, and generating photovoltaic power based on the light irradiated on the light receiving surface, wherein a second major surface of the semiconductor solar cell substrate is covered with a back-side insulating film composed of an inorganic insulating film having a cationic component thereof principally comprising silicon, and a back electrode is provided so as to cover the back-side insulating film so as to contact with the back surface of the semiconductor solar cell substrate through conductive portions penetrating the back-side insulating film, and
- the passivation characteristic of the insulating film can further be improved by surface-treating the inorganic insulating film, after. being deposited, by supplying the post-treatment gas to the surface thereof, while allowing the post-treatment gas to cause catalytic decomposition reaction with the aid of the heat catalyst, similarly to as in the above-described surface treatment.
- the post-treatment after the film formation proceeded in a hydrogen atmosphere under heating without using any catalyst, has already been known as hydrogen annealing, whereas the catalyst-assisted method of this invention is far superior thereto in the passivation effect.
- FIG. 1 is a schematic sectional view of the solar cell of this invention
- FIG. 2 is a schematic drawing of a film forming apparatus used for a method of fabricating the solar cell of this invention
- FIG. 3 is a schematic drawing of a batch-type, parallel-plate direct plasma CVD apparatus
- FIG. 4 is a schematic drawing of a single-wafer remote plasma CVD apparatus.
- FIG. 1 is a sectional view schematically showing the best mode for carrying out the solar cell of this invention.
- the solar cell 100 comprises a first-conductivity-type silicon single crystal substrate 66 (simply referred to as substrate 66 hereinafter; defined as p-type in this embodiment) as the semiconductor solar cell substrate, having on the first major surface of which a second-conductivity-type emitter layer 65 (defined as of n-type in this embodiment) formed thereon, and thereby having a p-n junction plane 167 in the in-plane direction.
- the emitter layer 65 has, as being formed on the major surface thereof, electrodes 63 for extracting output.
- the electrodes can be configured using Al, Ag or the like, as having a wide bus bar electrode reducing the internal resistance, formed at appropriate intervals, and finger electrodes branched from the bus bar electrode at predetermined intervals in a comb-like form.
- Non-formation area of the emitter layer 65 having no electrode 63 formed therein is covered with a light-receiving-surface-side insulating film 61 composed of silicon nitride.
- a second major surface (back surface) of the substrate 66 is covered with a back-side insulating film 62 composed of silicon nitride, and the entire surface of the back-side insulating film 62 is covered with back electrode 64 .
- the back electrode 64 is brought into electrical contact with the back surface of the substrate 66 through conductive portions (contact holes 67 ) penetrating the back-side insulating film 62 .
- Resistivity of the substrate is preferably adjusted to 0.1 ⁇ cm to 10 ⁇ cm, both ends inclusive, and more preferably 0.5 ⁇ cm to 2 ⁇ cm, both ends inclusive, in view of realizing a high-performance solar cell.
- the thickness of the substrate of as thick as 50 ⁇ m makes it possible to catch the incident light within the solar cell and is advantageous in terms of cost, but it is preferable to adjust it to 150 to 300 ⁇ m in view of ensuring a sufficient strength durable in the succeeding processes for the substrate.
- the light-receiving-surface-side insulating film 61 is configured as a low-hydrogen-content inorganic insulating film having a hydrogen content of 1 at % to 10 at %, more preferably 1 at % to 5 at %, both ends inclusive.
- Refractive index of the film is 2 to 2.5, both ends inclusive, allowing the film to be used also as an anti-reflection film.
- Si/N atomic ratio of the film is adjusted to 0.80 to 1.80, both ends inclusive.
- the back-side insulating film 62 is also configured as a silicon nitride film having a Si/N atomic ratio of 0.80 to 1.80, both ends inclusive (in this embodiment, the refractive index is 2 to 2.5, and the hydrogen content is 1 at % to 10 at %, more preferably 1 at % to 5 at %, both ends inclusive).
- Both of these films were formed by the catalytic CVD process in which a heat catalyst was placed together with the semiconductor solar cell substrate in a reaction vessel; and a film-forming gas, which comprised a silicon source gas and a nitrogen source gas, was supplied to the surface of the substrate while making the film-forming gas into contact with the heat catalyst, so as to deposit silicon nitride produced based on chemical reactions of the film-forming gas on the surface of the substrate.
- the reaction vessel 1 further comprises film forming gas introducing ducts 31 , 32 introducing film-forming gases thereinto, a surface treatment gas introducing duct 33 introducing a surface-treatment gas thereinto, heat catalyst 50 provided in the vessel so as to oppose with the substrate 20 on the substrate holder 21 , and the heat-catalyst-heating power source 51 heating, under current supply, the heat catalyst 50 .
- the evacuation device 11 comprises a multi-step vacuum pump comprising a turbo molecular pump, a rotary pump and so forth, and is designed to reduce the pressure in the process chamber to as low as about 10 ⁇ 8 Torr.
- the film forming gas introducing ducts 31 , 32 are connected to a disk-formed gas introducing head 35 introducing the film forming gas therethrough into the process chamber.
- the gas introducing head 35 has a hollow body, and has a number of gas blow holes on the front surface, so as to supply the film-forming gas through the gas blow holes down to the major surface (film forming surface) of the substrate 20 .
- Heat catalyst 50 is disposed on the flow path of the film-forming gas streaming from the gas introducing head 35 towards the substrate 20 , and is heated by a heat-catalyst-heating power source 51 to a catalyst activation temperature, to as high as 170° C., for example.
- the supplied film-forming gas reaches the major surface of the substrate while being made into contact with the heat catalyst 50 .
- the film forming gas under the contact therewith is enhanced to cause reactions such as decomposition so as to produce reaction active species, and allows an insulating material to deposit on the substrate 20 .
- Heat catalyst 50 in this embodiment is made of a tungsten wire having a diameter of 0.5 mm or around, processed to have a saw tooth form, for example, so as to cover an area wider than the substrate 20 .
- the substrate temperature may be as relatively low as 200° C. to 400° C., which is not causative of degradation in the contact characteristics with respect to the substrate 66 , even after the electrodes 63 , 64 are formed thereon.
- adoption of the catalytic CVD process using the heat catalyst 50 enables film formation without using plasma unlike the conventional process, so that any plasma damages on the surface of the substrate and degradation of the insulating film due to invasion of charged particles are avoidable by principle.
- Si/N atomic ratio of the silicon nitride film can be adjusted with the above-described range, by monitoring flow rates of silane and ammonia introduced respectively through the film forming gas introducing ducts 31 , 32 , such as a mass flow controller (not illustrated in the figure), and by controlling ratio of the flow rates using valves 31 v , 32 v .
- Silane and ammonia herein are not diluted by hydrogen gas.
- Heat catalyst 50 is also used for the surface treatment of the substrate prior to the film formation for the purpose of reducing interfacial defects.
- the surface of the substrate is generally covered with a native oxide film. Even if the native oxide film on the surface of the substrate 20 should preliminarily be removed using hydrofluoric acid or the like, oxidation readily proceeds under normal atmospheres, so that silicon atom species having oxygen atoms bonded thereto remain more or less on the surface of the substrate. For this reason, ammonia gas as the surface treatment gas is introduced, prior to formation of the insulating film, through the surface treatment gas introducing duct 33 via the introducing head 35 into the reaction vessel 1 .
- the ammonia gas is then converted into the active species by the catalytic decomposition reaction with the aid of heat catalyst 50 , and oxygen atoms (which possibly serve as sites for surface recombination) of the native oxide film covering the surface of the substrate are substituted by nitrogen atoms which are constituent atoms of the insulating film composed of silicon nitride.
- the film formation process of the insulating film is subsequently carried out by the catalytic CVD process already explained in the above. This method makes it possible to deposit the insulating film with less amount of interfacial defects while keeping the composition thereof uniform.
- the surface treatment gas introducing duct 33 is necessary for the purpose of carrying out the surface treatment, but it is allowable to use the film forming gas introducing duct 31 also as the surface treatment gas introducing duct, for the case where a gas, same as the film-forming gas, is used also as the surface treatment gas, such as the case in which the film-forming gas is a mixed gas of silane (silicon source gas) and ammonia (nitrogen source gas: anion source gas), and the surface treatment gas is ammonia gas.
- the nitrogen source gas, other than the ammonia gas, applicable to formation of the silicon nitride film may be nitrogen gas or any other nitrogen compound gas.
- the surface treatment gas is supplied to the substrate 20 through the gas introduction head 35 similarly to the film-forming gas, allowed to pass in the vicinity of the surface of the heat catalyst 50 so as to cause the catalytic decomposition reaction as described in the above, and thereby to promote the above-described surface treatment reaction for the substrate 20 .
- Heat catalyst 50 is also used for post-treatment for improving the passivation characteristics of the grown insulating film. More specifically, the characteristics of the insulating film can further be improved by introducing the post-treatment gas such as ammonia gas or hydrogen gas through the post-treatment gas introducing duct 34 after deposition of the insulating film, and by inducing the catalytic decomposition reaction with the aid of the heat catalyst 50 , similarly to as in the surface treatment, to thereby effect the post-treatment.
- the post-treatment gas such as ammonia gas or hydrogen gas
- the hydrogen content of the film may slightly increase during the post-treatment, but the amount of increase in most cases falls within a range from 1 at % to 3 at %, so that the final hydrogen content of the film never exceeds 10 at % so far as the hydrogen content of the as-deposited film is suppressed to as low as 5 at % or less.
- the etching generally adopts a mixture of sodium hydroxide and an alcohol, or an aqueous solution having potassium carbonate or sodium carbonate dissolved therein, producing the surface texture of as large as 1 to 10 ⁇ m.
- the incident light on the light-receiving surface is effectively introduced into the substrate, after being reflected multiple times by virtue of the texture.
- n + layer or the emitter layer 65 , is then formed.
- a Group V element represented by phosphorus
- the surface impurity concentration of the dopant in the n + layer is preferably adjusted so as to adjust the sheet resistance to 40 to 200 ⁇ / ⁇ .
- the back-side insulating film 62 composed of silicon nitride is then formed on the entire back surface of the substrate by the above-described catalytic CVD process, portions thereof corresponded to the contact holes 67 are then removed by a method such as photolithography, mechanical cutting, laser abrasion or the like, and the back electrode 64 typically composed of Al is deposited by the vacuum evaporation process, sputtering or the like.
- the passivation characteristics of general semiconductor devices are evaluated by forming a metal/insulator/semiconductor stacked structure (MIS structure) and by measuring the capacitance-voltage (C-V) characteristics.
- MIS structure metal/insulator/semiconductor stacked structure
- C-V capacitance-voltage
- effective recombination velocity is affected by interface state density, fixed charge in the film, electron- and hole-capture cross sections, substrate impurity concentration, carrier dose and so forth.
- the passivation performance on the light-receiving-surface side is evaluated based on performance of an actually fabricated solar cell.
- the conventional plasma CVD process was causative of a heavy plasma damage as described in the above, and it was therefore necessary to intentionally introduce a large amount of hydrogen into the film so as to terminate the dangling bonds.
- the plasma damage to the substrate is avoidable by forming the light-receiving-surface-side insulating film 61 by the catalytic CVD process, and thereby highly desirable passivation characteristics can be obtained.
- the temperature of film formation is preferably set to about 200° C. to 400° C., wherein the temperature as high as possible is preferable in view of the passivation characteristics, because defects in the film to be deposited will further be decreased. It is also preferable to keep the temperature of the substrate 66 below a temperature causative of thermal modification both in terms of material and of structure.
- the electrodes 63 are formed as Al electrodes on the light-receiving-surface-side insulating film 61 in a MIS contact manner, although being brought into contact with the emitter layer 65 in FIG. 1 , the temperature of film formation exceeding 400° C. results in spiking of the Al electrodes penetrating the emitter layer, to thereby degrade the performance due to short circuiting. It is therefore preferable to adjust the temperature of film formation to 400° C. or below.
- the temperature of the heat catalyst 50 is preferably equal to or lower than the catalyst temperature during the film formation, and is generally adjusted within a range from 1,000 to 1,700° C. Any post-treatment after the film formation is preferably carried out under the temperature of the heat catalyst 50 similar to the conditions of the surface treatment, wherein addition of, or substitution by the general hydrogen annealing is also allowable so far as the contact characteristics of the substrate, or between the electrodes and the substrate are not impaired.
- an effective lifetime was measured using a lifetime scanner while irradiating a white bias light of 0.5 sun, and the surface recombination velocity was calculated on the basis of a result of lifetime measurement of the same substrate but subjected to chemical passivation (iodine/ethanol treatment).
- a 400-W metal halogen lamp as a light source, one surface of the sample was exposed to ultraviolet radiation, from which wavelength component of 320 nm or shorter is cut by a filter, for 32 hours and 128 hours, and the surface recombination velocity was similarly calculated. Hydrogen content of the silicon nitride film was analyzed by the FT-IR method.
- the silicon substrate was cleaned and dried according to the procedures similar to as described in Experiment 1, and by the catalytic CVD process, the substrate was surface-treated using ammonia gas, on both surfaces of which the silicon nitride film having a refractive index of 2.4 was deposited, and then a similar measurement was carried out.
- the silicon substrate was cleaned and dried according to the procedures similar to as described in Experiment 1, and by the catalytic CVD process, the substrate was surface-treated using ammonia gas, on both surfaces of which the silicon nitride film having a refractive index of 2.4 was deposited, post-treated using hydrogen gas, and then a similar measurement was carried out.
- the silicon substrate was cleaned and dried according to the procedures similar to as described in Experiment 1, and on both surfaces of which the silicon nitride film having a refractive index of 2.4 was deposited by the direct plasma CVD process (frequency 100 kHz: without hydrogen dilution), and then the similar measurement was carried out.
- the silicon substrate was cleaned and dried according to the procedures similar to as described in Experiment 1, and on both surfaces of which the silicon nitride film having a refractive index of 2.4 was deposited by the remote plasma CVD process (microwave 2.5 GHz: without hydrogen dilution), and then the similar measurement was carried out.
- a quasi-square ( 100 ) single crystal silicon substrate (FZ process, B-doped) having a resistivity of 0.5 ⁇ cm, a thickness of 300 ⁇ m and a planar size of 100 mm ⁇ 100 mm was etched in a concentrated aqueous sodium hydroxide solution to remove damages, and on the entire surface of which a texture was formed in a mixed solution of aqueous sodium hydroxide solution/isopropanol.
- the substrate was subjected to the RCA cleaning, oxidized at a high temperature (1,000° C.), protected on one surface of which with a photo resist, and only one surface of the oxide film was etched in a buffered hydrofluoric acid solution.
- phosphorus was diffused at 830° C. using phosphorus oxychloride as a source so as to adjust sheet resistance of the surface to 100 ⁇ / ⁇ .
- a phosphorus glass formed on the surface was then removed using a 2% hydrofluoric acid, and light-receiving-surface side electrodes (Ti/Pd/Ag) were formed by vacuum evaporation through a mask.
- the back surface was subjected to machining to form trenches, and thereon the back electrode (Al) was vacuum-deposited.
- a quasi-square ( 100 ) single crystal silicon substrate (FZ process, B-doped) having a resistivity of 0.5 ⁇ cm, a thickness of 300 ⁇ m and a planar size of 100 mm ⁇ 100 mm was etched in a concentrated aqueous sodium hydroxide solution to remove damages, and on the entire surface of which a texture was formed in a mixed solution of aqueous sodium hydroxide solution/isopropanol.
- Two substrates were held back to back, and phosphorus was diffused at 830° C. using phosphorus oxychloride as a source so as to adjust sheet resistance of the surface to 100 ⁇ / ⁇ .
- a phosphorus glass formed on the surface was then removed using a 2% hydrofluoric acid, and light-receiving-surface side electrodes (Ti/Pd/Ag) were formed by vacuum evaporation through a mask.
- the solar cell was fabricated, and the characteristics thereof were evaluated by the measurement using a solar simulator (1.5 sun), similarly to as described in Example 7, except that the back surface was surface-treated using ammonia gas by the catalytic CVD process, a silicon nitride film having a refractive index of 2.0 and a thickness of 80 nm was deposited thereon, and the post-treatment was carried out using hydrogen gas.
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| PCT/JP2004/004405 WO2004100273A1 (ja) | 2003-05-09 | 2004-03-29 | 太陽電池及びその製造方法 |
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| US10/556,063 Abandoned US20070186970A1 (en) | 2003-05-09 | 2004-03-29 | Solar cell and method of fabricating the same |
| US12/656,360 Expired - Fee Related US8030223B2 (en) | 2003-05-09 | 2010-01-27 | Solar cell and method of fabricating the same |
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| US12/656,360 Expired - Fee Related US8030223B2 (en) | 2003-05-09 | 2010-01-27 | Solar cell and method of fabricating the same |
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| US (2) | US20070186970A1 (ja) |
| EP (1) | EP1630873A4 (ja) |
| JP (1) | JP4118187B2 (ja) |
| KR (1) | KR101058735B1 (ja) |
| CN (1) | CN100530700C (ja) |
| AU (1) | AU2004237524B2 (ja) |
| WO (1) | WO2004100273A1 (ja) |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1630873A4 (en) | 2007-03-14 |
| KR101058735B1 (ko) | 2011-08-22 |
| WO2004100273A1 (ja) | 2004-11-18 |
| JP2004335867A (ja) | 2004-11-25 |
| CN100530700C (zh) | 2009-08-19 |
| US20100173447A1 (en) | 2010-07-08 |
| CN1784789A (zh) | 2006-06-07 |
| KR20060064561A (ko) | 2006-06-13 |
| EP1630873A1 (en) | 2006-03-01 |
| AU2004237524A1 (en) | 2004-11-18 |
| US8030223B2 (en) | 2011-10-04 |
| JP4118187B2 (ja) | 2008-07-16 |
| AU2004237524B2 (en) | 2009-09-17 |
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