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WO2011051251A1 - Processus de gravure pour la production d'une matrice tft - Google Patents

Processus de gravure pour la production d'une matrice tft Download PDF

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Publication number
WO2011051251A1
WO2011051251A1 PCT/EP2010/066109 EP2010066109W WO2011051251A1 WO 2011051251 A1 WO2011051251 A1 WO 2011051251A1 EP 2010066109 W EP2010066109 W EP 2010066109W WO 2011051251 A1 WO2011051251 A1 WO 2011051251A1
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Prior art keywords
volume
mixture
etching
argon
silicon
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English (en)
Inventor
Marcello Riva
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Solvay Fluor GmbH
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Solvay Fluor GmbH
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Priority to JP2012535779A priority Critical patent/JP2013508990A/ja
Priority to CN2010800509172A priority patent/CN102754201A/zh
Publication of WO2011051251A1 publication Critical patent/WO2011051251A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • H01L21/31116—Etching inorganic layers by chemical means by dry-etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
    • H10D86/01—Manufacture or treatment
    • H10D86/021—Manufacture or treatment of multiple TFTs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • H01L21/32137—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas of silicon-containing layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
    • H10D86/40—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
    • H10D86/40—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs
    • H10D86/60—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs wherein the TFTs are in active matrices

Definitions

  • the present invention relates to a process for producing a thin film transistor (TFT) matrix for a liquid crystal display (LCD), and more particularly to a simplified back-channel-etch process for forming the TFT matrix with reduced masking steps and to gas mixtures, in particular suitable as etching gas for such process.
  • TFT thin film transistor
  • LCD liquid crystal display
  • the manufacture of a TFT matrix includes several steps of forming certain layers of matter, e.g. photoresist layers, conductive layers, etch stopper layers, semiconductor layers, and passivation layers. These layers are applied and then etched to obtain the TFT matrix. As is mentioned in US 6,406,928, etching of the passivation layer can be performed using trif uoromethane, while
  • semiconductor layers can be etched using carbon tetraf uoride, boron trichloride, chlorine, sulfur hexaf uoride or a mixture thereof.
  • etching agents have disadvantages.
  • trifluoromethane, carbon tetrafluoride and sulfur hexafluoride are considered disadvantageous for ecological reasons.
  • Object of the present invention is to provide an improved process for the manufacture of a thin film transistor (TFT) matrix for a liquid crystal display (LCD) and to provide an improved etching gas useful in his process.
  • TFT thin film transistor
  • LCD liquid crystal display
  • the process of the present invention for the manufacture of a TFT matrix includes at least one step wherein a layer is etched with a gaseous etching agent and wherein the etching agent comprises carbonyl fluoride (COF2), F2 or a mixture thereof.
  • COF2 carbonyl fluoride
  • Fluorine (F2) has no GWP and no impact on the ozone layer. It is very reactive, but not very selective, and thus, should be applied in diluted form. It can be used, for example, to etch tungsten (W).
  • Carbonyl fluoride has the advantage that it has a GWP of 1 and no impact on the ozone layer. It is very suitable in the frame of the present invention and is the preferred etching gas in the process of the present invention. In one particular embodiment, in particular when an etching gas comprising carbonyl fluoride is used, the etching gas is preferably free of elemental fluorine.
  • the etching agent comprises or consists of carbonyl fluoride. In another embodiment ; the etching agent comprises or consists of fluorine.
  • This embodiment is especially suitable for the fast etching of amorphous silicon or silicon nitride.
  • Mixtures comprising or consisting of fluorine or carbonyl fluoride and nitrogen or argon are very suitable for the etching of amorphous silicon or silicon nitride, and especially for the etching of silicon nitride.
  • carbonyl fluoride mixtures with at least one gas selected from the group consisting of nitrogen, argon, N 2 0 and oxygen is used as etching gas in the process according to the invention.
  • a mixture comprising or consisting of carbonyl fluoride, oxygen and argon is applied as etching gas.
  • a mixture comprising or consisting of carbonyl fluoride, N 2 0 and argon is applied as etching gas.
  • the etching step is plasma-assisted.
  • the process according to the invention is advantageously used when a layer formed of a material selected from the group consisting of silicon nitride, silicon oxide, silicon oxynitride and a combination of two or more thereof is etched. More advantageously, the process according to the invention is used when the layer comprises or consists of silicon nitride.
  • mixtures comprising carbonyl fluoride and N 2 0 and optionally argon and optionally oxygen are applied to the selective etching of a layer comprising or consisting of silicon nitride, silicon oxynitride and a combination of both on a layer of a-Si.
  • mixtures comprising or especially consisting of carbonyl fluoride, N 2 0 and argon, or mixtures comprising or especially consisting of carbonyl fluoride, N 2 0, oxygen and argon are applied.
  • Silicon is a fourfold coordinated atom that is normally tetrahedrally bonded to four neighboring silicon atoms. In crystalline silicon this tetrahedral structure continues over a large range, thus forming a well-ordered crystal lattice.
  • amorphous silicon denoted as a-Si or a-Si
  • this long range order is not present. Rather, the atoms form a continuous random network. Moreover, not all the atoms within amorphous silicon are fourfold coordinated. Due to the disordered nature of the material some atoms have a dangling bond.
  • a-Si denotes silicon in which the silicon atoms form a continuous random network.
  • N 2 0, oxygen or a mixture of N 2 0 and oxygen provides for the selectivity of the etch : when the silicon nitride layer which coats the a-Si layer is etched away, and the layer of a-Si comes into contact with the etching gas mixture, a-Si on the surface of the layer is oxidized in contact with N 2 0 and thus is passivated because a silicon oxide layer forms which protects the a-Si from being etched.
  • the process according to the invention is applied to etching a layer formed from a material selected from the group consisting of intrinsic amorphous silicon, micro-crystalline silicon and polysilicon.
  • Microcrystalline silicon also called nanocrystalline silicon contains small crystals. It absorbs a broader spectrum of light and is flexible.
  • Polycrystalline silicon or semi-crystalline silicon, polysilicon, poly-Si is a material consisting of multiple small silicon crystals.
  • the process according to the invention is applied to etching a layer formed of a material selected from the group consisting of highly doped amorphous silicon, highly doped micro-crystalline silicon and highly doped polysilicon is etched.
  • etch gas consisting of carbonyl fluoride, fluorine, or, preferably, by using mixtures consisting of carbonyl fluoride and argon and optionally nitrogen.
  • i is possible to perform a selective etching of silicon nitride, silicon oxynitride or mixtures thereof which are present as a coating over the intrinsic amorphous silicon, micro-crystalline silicon and polysilicon, highly doped amorphous silicon, highly doped micro-crystalline silicon and highly doped polysilicon by using
  • mixtures comprising carbonyl fluoride and N 2 0 and argon which provide a passivation of said Si when being in contact with the gas mixtures • mixtures comprising carbonyl fluoride, N2O and oxygen optionally in the presence of argon which provide a passivation of said Si when being in contact with the gas mixtures ;
  • a 6-mask process for example, may include steps of :
  • TAB tape automated bonding
  • ITO indium tin oxide
  • a substrate is provided made of an insulating material ; a first conductive layer is formed on a first side of the substrate, and a first masking and patterning procedure is used to remove a portion of the first conductive layer to define a scan line and a gate electrode of a TFT unit ; then, an insulation layer, a semiconductor layer, a doped semiconductor layer and a photoresist layer are successively formed on the substrate with the scan line and the gate electrode ; an exposing source is provided from a second side of the substrate opposite to the first side by using the scan line and the gate electrode as shields to obtain an exposed area and an unexposed area ; then the photoresist layer and the semiconductor layers of the exposed area are removed so that the remaining portion of the semiconductor layers in the unexposed area has a specific shape similar to the shape of the scan line together with the gate electrode ; a transparent conductive layer and a second conductive layer
  • the insulating material is a light-transmitting material such as glass.
  • each of the first and second conductive layers is formed of chromium, molybdenum, tantalum, tantalum molybdenum, tungsten molybdenum, aluminium, aluminium silicide, copper, or a combination thereof.
  • Etchants for these metals are known. Chromium and molybdenum can be etched by CCl 4 /0 2 plasma, copper by treatment with Cl 2 plasma and subsequently with a H 2 plasma, aluminium with a BCI3 plasma, tungsten with an F 2 plasma.
  • the insulation layer is formed of silicon nitride, silicon oxide, silicon oxynitride or a combination thereof.
  • the etch stopper layer is formed of silicon nitride, silicon oxide, or silicon oxynitride.
  • the semiconductor layer is formed of intrinsic amorphous silicon, micro-crystalline silicon or polysilicon
  • the doped semiconductor layer is formed of highly doped amorphous silicon, highly doped micro- crystalline silicon or highly doped polysilicon.
  • the transparent conductive layer is formed of indium tin oxide, indium zinc oxide or indium lead oxide.
  • the indium tin oxide (“ITO”) layer can be etched using HBr, optionally together with BCI3.
  • Indium zinc oxide (“IZO”) can be etched using an Ar/Cl 2 plasma.
  • the passivation layer is formed of silicon nitride or silicon oxynitride.
  • the third masking and patterning procedure additionally defines a plurality of TAB pad regions around the TFT matrix.
  • a portion of the second conductive layer surrounding the pixel electrode remains as a black matrix.
  • Etching gases containing carbonyl fluoride are suitable for performing the etching in the above mentioned steps of etching layers (passivating layers, insulating layers, and semiconductor layers). With etching gases containing carbonyl fluoride it is possible to create an isolation window as is outlined in figure 21 of US 6,406,928 under the reference sign 28.
  • the etching is expediently performed under plasma ; the plasma can be direct plasma (in situ plasma) or a remote plasma or a combination of both.
  • Carbonyl fluoride can be applied as neat substance or in admixture with other active or inert gases, for example, with nitrogen or helium. It is preferably applied together with argon. If a layer of silicon nitride has to be etched selectively over a layer of a-silicon or other forms of silicon, the etching gas mixture comprises additionally oxygen and/or N 2 0 ; nitrogen is not necessary. As mentioned above, oxygen and nitrogen oxide provide a passivating layer of silicon oxide on the layer of a-silicon as soon as the coating layer of silicon nitride is etched away.
  • carbonyl fluoride preferably may be contained in an amount of equal to or more than 50 % by volume, preferably equal to or less than 79 % by volume. The remainder to 100 % by volume is preferably constituted by oxygen, argon and/or N 2 0.
  • Mixtures comprising or consisting of carbonyl fluoride and argon are preferably applied for fast etching ; mixtures comprising or consisting of carbonyl fluoride and N 2 0, mixtures comprising or consisting of carbonyl fluoride and oxygen, mixtures comprising or consisting of carbonyl fluoride, oxygen and argon, mixtures comprising or consisting of carbonyl fluoride, N 2 0 and argon, and mixtures comprising carbonyl fluoride, oxygen, nitrogen oxide and argon are very preferably applied as etching gas for selective etching of layers which coat silicon, especially for silicon nitride layers which coat a-silicon.
  • the content of carbonyl fluoride may preferably be equal to or greater than 50 % by volume especially in the beginning of the selective etching of the silicon nitride layer when there is no risk that the a-silicon comes into contact with the etching gas. Even neat carbonyl fluoride or a mixture of carbonyl fluoride with argon, without passivating oxygen or passivating N 2 0 may be applied. In later stages of the etching process when the layer of nitrogen oxide is partially etched away, carbonyl fluoride preferably may be contained in an amount of equal to or less than 50 % by volume, and in an amount preferably equal to or more than 15 % by volume. N 2 0, and if present, oxygen and argon, respectively, are the balance to 100 % by volume. Hereby it is safeguarded that the silicon nitride is etched selectively over a-silicon.
  • the concentration of F 2 or COF 2 in the initial stage of the etching process is higher than in the final stage.
  • the invention also relates to certain mixtures comprising or consisting of carbonyl fluoride or fluorine and N 2 0 and optionally argon wherein the content of carbonyl fluoride or fluorine is preferably equal to or greater than 50 % by volume ; and to mixtures comprising or consisting of carbonyl fluoride or fluorine, oxygen and N 2 0 and optionally argon wherein the content of carbonyl fluoride or fluorine is preferably equal to or greater than 50 % by volume. These mixtures preferably are produced in situ in a tool wherein they are applied.
  • fluorine gas or carbonyl fluoride and N 2 0 and optionally argon are fed to the tool which may, for example, be an etching chamber for TFTs or photovoltaic cells.
  • these mixtures can be prepared in a conventional manner by providing them into a container, preferably under a pressure of equal to or greater than 1.5 bar (abs.) and preferably equal to or lower than 15 bar (abs.).
  • the mixtures preferably have a pressure of 0.1 mbar (abs.) to 15 bar (abs.).
  • carbonyl fluoride is the preferred etching agent.
  • the invention also relates to certain mixtures comprising or consisting of carbonyl fluoride or fluorine and N 2 0 and optionally argon wherein the content of carbonyl fluoride or fluorine is preferably equal to or lower than 50 % by volume ; and to certain mixtures comprising or consisting of carbonyl fluoride or fluorine, oxygen and N 2 0 and optionally argon wherein the content of carbonyl fluoride or fluorine is preferably equal to or lower than 50 % by volume. These mixtures preferably are produced in situ in a tool wherein they are applied.
  • Appropriate amounts of fluorine gas or carbonyl fluoride and N 2 0 are fed to the tool which may, for example, be an etching chamber for TFTs or photovoltaic cells.
  • the content of F 2 or COF 2 in this embodiment is preferably equal to or greater than 15 % by volume.
  • the mixtures preferably have a pressure of 0.1 mbar (abs.) to 15 bar (abs.). These mixtures are very suitable in the final stages of a process for the selective etching of silicon nitride layers, especially of silicon layers over a- silicon when the a-silicon is close to a contact with the etching gas.
  • the mixture according to the invention is a mixture comprising or consisting of carbonyl fluoride and N 2 0 or a mixture consisting of carbonyl fluoride, N 2 0 and argon.
  • the COF 2 content is generally equal to or greater than 50 % by volume.
  • the content of argon preferably is 0 to 20 % by volume.
  • N 2 0 and N 2 0 and argon, respectively, constitute the balance to 100 % by volume.
  • These mixtures are especially suitable, as described above, for the selective etching of silicon nitride coatings over a-silicon in initial stages of the etching process. Typical examples of these mixtures are compiled in table 1.
  • the mixture according to the invention is a mixture comprising or consisting of carbonyl fluoride and N 2 0 or a mixture consisting of carbonyl fluoride, N 2 0 and argon.
  • the COF 2 content is generally equal to or lower than 50 % by volume.
  • the content of argon preferably is 0 to 20 % by volume.
  • N 2 0 and N 2 0 and argon, respectively, constitute the balance to 100 % by volume.
  • the content of carbonyl fluoride is preferably equal to or greater than 15 % by volume.
  • the mixtures according to the invention further comprise oxygen.
  • the content of carbonyl fluoride is as given above
  • the content of argon is preferably 0 to 20 % by volume
  • the sum of the content of oxygen and N 2 0 in the gas mixture is is the balance to 100 % by volume.
  • the content of oxygen and N 2 0 sum up to the balance to 100 % by volume.
  • the content of oxygen is > 0 % by volume
  • the content of N 2 0 is > than 0.
  • the molar ratio of 0 2 : N 2 0 is 0.1 : 1 to 1 :0.1.
  • the mixture may also comprise nitrogen ; preferably, they do not contain nitrogen.
  • the content of carbonyl fluoride is equal to or greater than 50 % by volume. Preferably, it is equal to or lower than 90 % by volume.
  • the oxygen content is preferably greater than 0 % by volume and equal to or lower than 20 % by volume.
  • N 2 0 and, if present, argon are the balance to 100 % by volume.
  • the content of carbonyl fluoride is ⁇ 50 % by volume. Preferably, it is equal to or greater than 15 % by volume.
  • the oxygen content is preferably greater than 0 % by volume and equal to or lower than 20 % by volume.
  • N 2 0 and, if present, argon are the balance to 100 % by volume.
  • mixtures of the present invention are liquid mixtures comprising carbonyl fluoride and N 2 0 and optionally other gases, e.g. nitrogen or especially argon or oxygen.
  • the mixtures are gaseous.
  • the pressure may be equal to or greater than 0.1 mbar (abs) up to equal to or lower than 15 bar (abs.).
  • the gas mixtures preferably have a pressure of equal to or greater than 0.1 mbar (abs) up to equal to or lower than 1 bar (abs.) if the are provided or prepared in situ in the etching tool. They preferably have a pressure of > 1 bar (abs.) to equal to or lower than 15 bar (abs.) if they are stored in a storage container.
  • the mixture according to the invention is a mixture comprising or consisting of fluorine and N 2 0 or a mixture consisting of fluorine, N 2 0 and argon.
  • the F 2 content is generally equal to or greater than 50 % by volume.
  • the content of argon preferably is 0 to 20 % by volume.
  • N 2 0 and N 2 0 and argon, respectively, constitute the balance to 100 % by volume.
  • the mixture according to the invention is a mixture comprising or consisting of fluorine and N 2 0 or a mixture consisting of fluorine, N 2 0 and argon.
  • the F 2 content is generally equal to or lower than 50 % by volume.
  • the content of argon preferably is 0 to 20 % by volume.
  • N 2 0 and N 2 0 and argon, respectively, constitute the balance to 100 % by volume.
  • the content of fluorine preferably is equal to or greater than 25 % by volume.
  • the mixture according to the invention comprising fluorine further comprises oxygen.
  • the content of oxygen in the gas mixture is generally from>0 to 20 by volume and N 2 0 and, if present, argon, is the balance to 100 % by volume.
  • the mixture according to the invention is a mixture comprising or consisting of F 2 and N 2 0 or a mixture consisting of F 2 , N 2 0 and argon.
  • the F 2 content is generally equal to or greater than 50 % by volume.
  • the content of argon preferably is 0 to 20 % by volume.
  • N 2 0 and N 2 0 and argon, respectively, constitute the balance to 100 % by volume.
  • These mixtures are especially suitable, as described above, for the selective etching of silicon nitride coatings over a-silicon in initial stages of the etching process. Typical examples of these mixtures are compiled in table 5.
  • Table 5 Etching gas mixtures with F 2 > 50 % by volume (amounts given in % by volume)
  • the mixture according to the invention is a mixture comprising or consisting o F 2 and N 2 0 or a mixture consisting of F 2 , N 2 0 and argon.
  • the F 2 content is generally equal to or lower than 50 % by volume.
  • the content of argon preferably is 0 to 20 % by volume.
  • N 2 0 and N 2 0 and argon, respectively, constitute the balance to 100 % by volume.
  • the content of F 2 is preferably equal to or greater than 15 % by volume.
  • the mixtures according to the invention further comprise oxygen.
  • the content of F 2 is as given above, the content of argon is preferably 0 to 20 % by volume, and the sum of the content of oxygen and N 2 0 in the gas mixture is is the balance to 100 % by volume.
  • the contents of oxygen and N 2 0 sum up to the balance to 100 % by volume.
  • the content of oxygen is > 0 % by volume, and also the content of N 2 0 is > than 0.
  • the molar ratio of 0 2 : N 2 0 is 0.1 : 1 to 1 :0.1.
  • the mixture may also comprise nitrogen ; preferably, they do not contain nitrogen.
  • the content of F 2 is equal to or greater than 50 % by volume. Preferably, it is equal to or lower than 90 % by volume.
  • the oxygen content is preferably greater than 0 % by volume and equal to or lower than 20 % by volume.
  • N 2 0 and, if present, argon are the balance to 100 % by volume.
  • the content of F 2 is ⁇ 50 % by volume. Preferably, it is equal to or greater than 15 % by volume.
  • the oxygen content is preferably greater than 0 % by volume and equal to or lower than 20 % by volume.
  • N 2 0 and, if present, argon are the balance to 100 % by volume.
  • compositions indicated in the above tables 1 to 8 are preferred compositions but which can also be the upper or lower limit of a range of preferred compositions. As such the limits in the table are combinable to disclose preferred ranges of compositions according to the invention.
  • An empty field discloses 0 vol % of the respective gas.
  • the mixtures are gaseous unless they cooled to condense the F 2 .
  • the pressure may be equal to or greater than 0.1 mbar (abs) up to equal to or lower than 15 bar (abs.).
  • the gas mixtures preferably have a pressure of equal to or greater than 0.1 mbar (abs) up to equal to or lower than 1 bar (abs.) if they are provided or prepared in situ in the etching tool. They preferably have a pressure of > 1 bar (abs.) to equal to or lower than 15 bar (abs.) if they are stored in a storage container.
  • the mixtures can be prepared in the tool in situ by providing respective separate gas streams into the tool. Alternatively, they can be premixed before feeding them into the tool.
  • mixtures obtained by providing carbonyl fluoride in a flow of 400 seem, nitrogen oxide in a flow of 50 seem, and a flow of argon are excluded, and preferably mixtures having a pressure of 1 mbar obtained by providing carbonyl fluoride in a flow of 400 seem, nitrogen oxide in a flow of 50 seem, and a flow of argon are excluded.
  • the invention also concerns the use of the mixture according to the invention, as etching gas or cleaning gas.
  • the mixtures are suitably used to etch a material preferably selected from the group consisting of silicon nitride, silicon oxide or silicon oxynitride, a-Si intrinsic amorphous silicon, micro-crystalline silicon and polysilicon,highly doped amorphous silicon, highly doped micro- crystalline silicon and highly doped polysilicon. They are particularly suitable in the process according to the invention.
  • the invention also concerns the use of the mixture according to the invention as SF 6 replacement or NF 3 replacement.
  • Carbonyl fluoride and any other gases applied jointly can be introduced separately from each other into the plasma chamber.
  • carbonyl fluoride is mixed with other gases, e.g. nitrogen, oxygen, argon and/or N 2 0, before being introduced into the plasma chamber.
  • gases e.g. nitrogen, oxygen, argon and/or N 2 0
  • Introducing a homogenous premix is preferred because it guarantees fixed conditions to start the in situ plasma in the plasma chamber.
  • the layer forming steps and etching steps can be performed in known apparatus, for example, in PECVD tools of AKT, Inc, a subsidiary of Applied Materials, Inc.
  • the plasma-induced etching treatment is often performed at reduced pressure. Pressure is given in the following in absolute values.
  • the pressure is equal to or higher than 0.1 mbar. Preferably, it is equal to or lower than 100 mbar. Especially preferably, it is equal to or lower than 50 mbar.
  • the etching treatment is performed for a time which is sufficient to provide the desired degree of etching.
  • the treatment is performed for equal to or more than 1 second.
  • the treatment is performed for equal to or less than 10 minutes, preferably for equal to or less than 5 minutes.
  • the gases leaving the plasma reactor comprise unreacted etchant, HF, SiF 4 or metal fluorides and other reaction products.
  • the off gas can be washed with water, especially alkaline water, to remove any HF, carbonyl fluoride, SiF 4 or fluorine, and precipitate metal fluorides. Any oxygen, nitrogen, helium or argon passing the washer can be recovered or passed to the environment.
  • the simple removal of HF, carbonyl fluoride and fluorine in alkaline water or by other well- known methods compared with other etching gases is a further advantage.
  • Example 1 Production of an etchant gas mixture containing oxygen
  • Carbonyl fluoride, oxygen and argon in a volume ratio of 70, 10 and 20 are introduced under pressure into a steel cylinder.
  • the gas mixture can be applied as etching composition for TFT matrices.
  • Example 2 Production of an etchant gas mixture containing N 2 0
  • Carbonyl fluoride, N2O and argon in a volume ratio of 70, 20 and 10 are introduced under pressure into a steel cylinder.
  • the gas mixture can be applied as etching composition for TFT matrices.
  • SiN x is deposited via a PECVD process on a glass plate.
  • the plate is then patterned with a photoresist brought into a plasma etch tool.
  • the tool is evacuated, the gas mixture of example 2 is introduced into the tool ; the pressure is regulated to 1 mbar, and the plasma is switched on. After 1 minute, nitrogen is introduced into the tool, and the etched sample is taken out of the tool.
  • the SiN x is etched.
  • Example 4 Etching of SiN x with premixed gas containing oxygen
  • SiN x is deposited via a PECVD process on a glass plate.
  • the plate is then patterned with a photoresist brought into a plasma etch tool.
  • the tool is evacuated, the gas mixture of example 1 is introduced into the tool ; the pressure is regulated to 1 mbar, and the plasma is switched on. After 1 minute, nitrogen is introduced into the tool, and the etched sample is taken out of the tool.
  • the SiN x is etched.
  • SiN x is deposited via a PECVD process on a glass plate.
  • the plate is then patterned with a photoresist and brought into a plasma etch tool.
  • the tool is evacuated.
  • Carbonyl fluoride, oxygen and nitrogen are stored in separate steel cylinders. They are introduced in a volume ratio of 70, 10 and 20 into a common line which is connected to the plasma tool.
  • the resulting gas mixture is introduced into the tool ; the pressure is regulated to 1 mbar, and the plasma is switched on. After 1 minute, nitrogen is introduced into the tool, and the etched sample is taken out of the tool.
  • the SiN x is etched.
  • SiN x is deposited via a PECVD process on a glass plate.
  • the plate is then patterned with a photoresist and brought into a plasma etch tool.
  • the tool is evacuated.
  • Carbonyl fluoride, N 2 0 and nitrogen are stored in separate steel cylinders. They are introduced in a volume ratio of 70, 20 and 10 into a common line which is connected to the plasma tool.
  • the resulting gas mixture is introduced into the tool ; the pressure is regulated to 1 mbar, and the plasma is switched on. After 1 minute, nitrogen is introduced into the tool, and the etched sample is taken out of the tool.
  • the SiN x is etched.
  • Si0 2 is deposited via a PECVD process on a glass plate.
  • the plate is then patterned with a photoresist brought into a plasma etch tool.
  • the tool is evacuated, the gas mixture of example 2 is introduced into the tool ; the pressure is regulated to 1 mbar, and the plasma is switched on. After 1 minute, nitrogen is introduced into the tool, and the etched sample is taken out of the tool.
  • the Si0 2 is etched.
  • Example 8 Etching of Si0 2 with oxygen containing gas mixture produced immediately before its application Si0 2 is deposited via a PECVD process on a glass plate. The plate is then patterned with a photoresist and brought into a plasma etch tool. The tool is evacuated. Carbonyl fluoride, oxygen and nitrogen are stored in separate steel cylinders. They are introduced in a volume ratio of 70, 10 and 20 into a common line which is connected to the plasma tool. The resulting gas mixture is introduced into the tool ; the pressure is regulated to 1 mbar, and the plasma is switched on. After 1 minute, nitrogen is introduced into the tool, and the etched sample is taken out of the tool. The Si0 2 is etched.
  • Si0 2 is deposited via a PECVD process on a glass plate.
  • the plate is then patterned with a photoresist and brought into a plasma etch tool.
  • the tool is evacuated.
  • Carbonyl fluoride, N 2 0 and nitrogen are stored in separate steel cylinders. They are introduced in a volume ratio of 70, 20 and 10 into a common line which is connected to the plasma tool.
  • the resulting gas mixture is introduced into the tool ; the pressure is regulated to 1 mbar, and the plasma is switched on. After 1 minute, nitrogen is introduced into the tool, and the etched sample is taken out of the tool.
  • the Si0 2 is etched.
  • Amorphous silicon is deposited via a PECVD process on a glass plate.
  • the plate is then patterned with a photoresist and brought into a plasma etch tool.
  • the tool is evacuated, the gas mixture of example 1 is introduced into the tool ; the pressure is regulated to 1 mbar, and the plasma is switched on.
  • Example 11 Etching of amorphous silicon with oxygen containing gas mixture produced immediately before its application
  • Amorphous silicon is deposited via a PECVD process on a glass plate.
  • the plate is then patterned with a photoresist and brought into a plasma etch tool.
  • the tool is evacuated.
  • Carbonyl fluoride, oxygen and nitrogen are stored in separate steel cylinders. They are introduced in a volume ratio of 70, 10 and 20 into a common line which is connected to the plasma tool.
  • the resulting gas mixture is introduced into the tool ; the pressure is regulated to 1 mbar, and the plasma is switched on. After 1 minute, nitrogen is introduced into the tool, and the etched sample is taken out of the tool.
  • the silicon is etched.
  • Example 12 Etching of a silicon nitride layer over a layer of amorphous silicon with F 2 /N 2 0
  • a layer of silicon nitride is deposited via a PECVD process on a layer of amorphous silicon.
  • pure F 2 is supplied to the etching chamber with a flow rate of 200 seem.
  • a high frequency power of 600 Watt at 13.56 MHz is supplied to the plasma tool.
  • N 2 0 is additionally passed into the tool with a flow rate of 40 to 60 seem.
  • the flow of N 2 0 is increased to 500 seem. The etching process can be stopped when the desired etching of silicon nitride is achieved.
  • Example 13 Etching of a silicon nitride layer over a layer of amorphous silicon with F 2 /N 2 0 in the presence of argon
  • a layer of silicon nitride is deposited via a PECVD process on a layer of amorphous silicon.
  • F 2 and argon are supplied to the etching chamber with a flow rate of 200 seem (F 2 ) and 40 seem (argon).
  • a high frequency power of 600 Watt at 13.56 MHz is supplied to the plasma tool.
  • N 2 0 is additionally passed into the tool with a flow rate of 40 to 60 seem.
  • the flow of N 2 0 is increased to 500 seem.
  • the etching process can be stopped when the desired etching of silicon nitride is achieved.
  • Example 14 Etching of a silicon nitride layer over a layer of amorphous silicon with COF 2 /N 2 O
  • a layer of silicon nitride is deposited via a PECVD process on a layer of amorphous silicon.
  • pure COF 2 is supplied to the etching chamber with a flow rate of 200 seem.
  • a high frequency power of 600 Watt at 13.56 MHz is supplied to the plasma tool.
  • N 2 O is additionally passed into the tool with a flow rate of 40 to 60 seem and is increased to 600 seem.
  • the etching process can be stopped when the desired etching of silicon nitride is achieved.
  • Example 15 Etching of a silicon nitride layer over a layer of amorphous silicon with COF 2 /N 2 O in the presence of argon
  • a layer of silicon nitride is deposited via a PECVD process on a layer of amorphous silicon.
  • COF 2 and argon are supplied to the etching chamber with a flow rate of 200 seem (F 2 ) and 40 seem (argon).
  • a high frequency power of 600 Watt at 13.56 MHz is supplied to t he plasma tool.
  • N 2 O is additionally passed into the tool with a flow rate of 40 to 60 seem and the flow is gradually increased to 600 seem.
  • the etching process can be stopped when the desired etching of silicon nitride is achieved.
  • premixed gas mixtures is that high homogeneity is safeguarded, and the application is simpler, obviating the mixing of the constituents.
  • the advantage of using gas mixtures immediately produced before their introduction into the plasma tool is a higher flexibility and preciseness concerning the amounts of the constituents.
  • the etching of silicon nitride layers on amorphous silicon may be performed advantageously by initially applying etching gas with a higher concentration of COF 2 or F 2 and adding N 2 0 and/or oxygen in later stages of the etching process as described above.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Drying Of Semiconductors (AREA)
  • Thin Film Transistor (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

La présente invention concerne une matrice de transistor à couches minces (TFT) destinée à un écran à cristaux liquides (LCD). La matrice peut être préparée grâce à la réalisation de plusieurs étapes consistant à former des couches, et de plusieurs étapes consistant à graver partiellement ces couches. Du fluor, de préférence du fluorure de carbonyle, conjugué préférentiellement à de l'oxygène, du N2O et/ou de l'argon, est utilisé comme gaz de gravure. La présente invention concerne également un mélange gazeux constitué de F2 ou de fluorure de carbonyle, de N2O et éventuellement d'argon.
PCT/EP2010/066109 2009-10-26 2010-10-26 Processus de gravure pour la production d'une matrice tft Ceased WO2011051251A1 (fr)

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JP2012535779A JP2013508990A (ja) 2009-10-26 2010-10-26 Ｔｆｔマトリックスを製造するためのエッチングプロセス
CN2010800509172A CN102754201A (zh) 2009-10-26 2010-10-26 用于生产tft基质的蚀刻方法

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EP2871669A1 (fr) * 2013-11-07 2015-05-13 Solvay SA Mélange gaz et cuve de transport adaptée
EP2944385A1 (fr) 2014-05-12 2015-11-18 Solvay SA Procédé de gravure et de nettoyage d'une chambre et gaz associé
EP3038142A1 (fr) * 2014-12-18 2016-06-29 LAM Research Corporation Gravure de nitrure sélective
US9837286B2 (en) 2015-09-04 2017-12-05 Lam Research Corporation Systems and methods for selectively etching tungsten in a downstream reactor
US9911620B2 (en) 2015-02-23 2018-03-06 Lam Research Corporation Method for achieving ultra-high selectivity while etching silicon nitride
US10147588B2 (en) 2016-02-12 2018-12-04 Lam Research Corporation System and method for increasing electron density levels in a plasma of a substrate processing system
US10192751B2 (en) 2015-10-15 2019-01-29 Lam Research Corporation Systems and methods for ultrahigh selective nitride etch
US10410832B2 (en) 2016-08-19 2019-09-10 Lam Research Corporation Control of on-wafer CD uniformity with movable edge ring and gas injection adjustment
US10438833B2 (en) 2016-02-16 2019-10-08 Lam Research Corporation Wafer lift ring system for wafer transfer
US10453986B2 (en) 2008-01-23 2019-10-22 Solvay Fluor Gmbh Process for the manufacture of solar cells
US10651015B2 (en) 2016-02-12 2020-05-12 Lam Research Corporation Variable depth edge ring for etch uniformity control
US10699878B2 (en) 2016-02-12 2020-06-30 Lam Research Corporation Chamber member of a plasma source and pedestal with radially outward positioned lift pins for translation of a substrate c-ring
US10825659B2 (en) 2016-01-07 2020-11-03 Lam Research Corporation Substrate processing chamber including multiple gas injection points and dual injector
US10957561B2 (en) 2015-07-30 2021-03-23 Lam Research Corporation Gas delivery system
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US12183554B2 (en) 2017-11-21 2024-12-31 Lam Research Corporation Bottom and middle edge rings
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US10453986B2 (en) 2008-01-23 2019-10-22 Solvay Fluor Gmbh Process for the manufacture of solar cells
EP2549526A1 (fr) * 2011-07-18 2013-01-23 Solvay Sa Procédé de fabrication d'éléments gravés à l'acide utilisant des composés fluoro-substitués
EP2549525A1 (fr) * 2011-07-18 2013-01-23 Solvay Sa Procédé de fabrication d'éléments gravés à l'acide utilisant le CHF3
EP2871669A1 (fr) * 2013-11-07 2015-05-13 Solvay SA Mélange gaz et cuve de transport adaptée
WO2015067541A1 (fr) * 2013-11-07 2015-05-14 Solvay Sa Réservoir de transport de gaz
EP2944385A1 (fr) 2014-05-12 2015-11-18 Solvay SA Procédé de gravure et de nettoyage d'une chambre et gaz associé
EP3038142A1 (fr) * 2014-12-18 2016-06-29 LAM Research Corporation Gravure de nitrure sélective
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US9911620B2 (en) 2015-02-23 2018-03-06 Lam Research Corporation Method for achieving ultra-high selectivity while etching silicon nitride
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US20230290643A1 (en) * 2020-07-09 2023-09-14 Showa Denko K,K, Etching method and semiconductor element manufacturing method
US12500068B2 (en) 2023-10-05 2025-12-16 Lam Research Corporation Edge rings providing kinematic coupling and corresponding substrate processing systems

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