TWI414625B - The transparent conductive oxides (tcos) thin films were deposited by atomic layer deposition (ald) technology - Google Patents

Abstract

The transparent conductive oxides (TCOs) thin films were deposited by atomic layer deposition (ALD) technology which had a good uniformity in thickness, crystalline structure and film quality. The method can be applied to the fabrication of electrical devices, such as flat panel displays, touch panel displays, ICs, photovoltaic cells, and the other industries which use TCOs.

Description

Method for forming transparent conductive film by atomic layer deposition method

The present invention utilizes atomic layer deposition (ALD) technology to complete the preparation of transparent conducting oxides (TCOs) and devices. The ALD technology can precisely control the ratio of main metal, oxygen atom and doping metal element in metal oxide, with good coating uniformity, precise coating layer thickness and thickness and composition control ability. Moreover, the ALD technology has a mild process and does not have the problem of ion bombardment. The process of fabricating the component does not harm the problem of depositing the film, and the transparent conductive film can be applied to the stacking of the upper and lower cells in the tandem solar cell. The middle layer (interlayer).

Transparent conductive films occupy an important position in the applications of flat panel displays, touch panels, integrated circuits and solar energy. Indium tin oxide ITO (In ₂ O ₃ :SnO ₂ ) is a transparent conductive film mainly used at present. Many transparent conductive films are derived from ITO due to different industrial application requirements, such as indium oxide titanium ITiO (In ₂ O ₃ :TiO _{2 ).} Indium oxide molybdenum IMO (In ₂ O ₃ :MoO ₃ ), indium oxide tungsten IWO (In ₂ O ₃ : WO ₃ ), and indium gallium oxide IGO (In ₂ O ₃ :Ga ₂ O ₃ ). IGO in the non-patent literature Appl. Phys. Lett., 65, 1 (1994) uses vacuum DC reactive sputtering and electrospray deposition to form IGO, but does not use ALD to form IGO; in the non-patented literature Applied ALD is used to form ITO in Surface Science, 99, 91-98 (1996), but IGO is not formed by the method of ALD; in Non-Patent Document J. Mater. Chem., 6(1), 27-31 (1996), . Chem.Mater, 18,471-475 (2006), Integrated Ferroelectrics, 80,197-206 (2006) using ALD ₂ O ₃ to form a gallium oxide Ga, but not formed using the ALD method IGO; Ferroelectrics 85,155- in Non-Patent Document Integrated ALD (2006) uses ALD to form titanium oxide gallium GaTiO ₂ , but does not form IGO using ALD; in the non-patent literature Superlattices and Micro structures 42, 172-175 (2007), ALD is used to form zinc gallium oxide GaZnO, but There is no method of forming IGO by using ALD; another class of zinc oxide (ZnO) as a transparent conductive film material is widely expected because zinc (Zn) is abundant and inexpensive, and is non-toxic. However, the resistance of pure ZnO is too high, so other metal elements are added for doping to increase the carrier concentration and conductivity, such as zinc aluminum oxide AZO (ZnO: Al ₂ O ₃ ), zinc gallium oxide GZO (ZnO: Ga ₂ O ₃ ) Zinc oxide zirconium ZZO (ZnO: ZrO ₂ ), wherein the transparent conductive film of ZZO is prepared by electro-electron pulse deposition method in Non-Patent Document Appl. Phys. Lett., 83, 18 (2003); Patent Document Applied Surface Science 252, 2006-2011 (2005), Applied Surface Science 252, 5687-569 (2006), Applied Surface Science 254, 6983-6986 (2008), Thin Solid Film 516, 2017-2021 (2008) The ZZO film was formed by RF magnetron sputtering, but the ALD method was not used to form the ZZO. A ZZO film is formed by a sol-gel method (Sol-gel) of a wet chemical film formation method in Non-Patent Literature Materials Chemistry and Physics 79, 71-75 (2003), but no ALD method is used to form ZZO.

In a combined electronic component, a conductive film is often required between the component and the component for bonding between the components. The film can be generally prepared by evaporation or sputtering, but sputtering. There are problems with ion bombardment, so the process of making components often hurts the existing deposited film and affects the performance of the component. The ALD technology has a mild process and no ion bombardment damage. It has the problem of depositing thin films and is suitable for the deposition of conductive layers between stacked components. The deposited film has good quality, high density, minimal defects and impurities, and stepped over. Sex is also good. The use of ALD to form IGO and zinc zirconium zirconia ZZO (ZnO: ZrO ₂ ) transparent conductive film can accurately control the number and thickness of thin film deposited layers, and can accurately control the ratio of metal, oxygen and doping metal elements in the transparent conductive film. Conductivity and visible light penetration adjust the elasticity to achieve the level of practical use.

The main object of the present invention is to provide a method for forming a transparent conductive film by atomic layer deposition, which can be applied to electrodes and electrical conductors of electronic components of solar cells, such as tandem conductive lines and stacked types between solar cells ( Tandem) solar battery upper and lower battery Stacked interlayer electrical conductive film. Controlling the intermediate layer can increase the reflection of light under appropriate layers and thicknesses, can reduce the thickness of amorphous silicon, reduce the severity of light decay, and help improve the overall light energy conversion efficiency of stacked solar cells. And stability.

Another object of the present invention is to provide a method for forming a transparent conductive film by atomic layer deposition. The transparent conductive film formed by the method can be applied to a flat panel display, a touch panel, a solar energy industry, an integrated circuit, and the like. The industry of transparent conductive films.

The invention provides a method for manufacturing a transparent metal oxide conductive film, which is characterized in that the atomic layer deposition technology precisely controls the number of deposited layers and the thickness of the transparent conductive film and the ratio of metal, oxygen and doping metal elements in the film. First, the clean substrate is placed in the reaction chamber, and the first reactant is used in the container in the first cycle, the reactants may be solid, the liquid and the gas may be heated through the heating device of the container, and the reactants become gaseous and enter the reaction. The chamber is chemically or physically reacted with the substrate to form a film on the substrate, or may be heated on the substrate at 50 to 500 ° C, and the unreacted material is taken out of the reaction chamber by using nitrogen or an inert gas to clean the reaction. a second injection of the oxygen-containing reactant with the first reactant by chemisorption or physical adsorption to form a film of the atomic layer, and the second oxygen-containing reactant and the first reactant are chemically adsorbed or physically adsorbed. The reactants that form the film are adsorbed and removed using nitrogen or inert gas to the reaction chamber. The second cycle uses a third reactant in a vessel, the reactants can be solids, liquids and gases can be heated via heating means outside the vessel, causing the reactants to enter the reaction chamber in a gaseous state, producing a chemical or physical reaction with the substrate. After film formation on the substrate, it can also be heated on the substrate at 50-500 ° C. The unreacted material is taken out of the reaction chamber by using nitrogen or an inert gas to clean the reaction chamber and then inject a fourth oxygen-containing one. The reactant and the third reactant are chemically adsorbed or physically adsorbed to form a thin film of the atomic layer, and the fourth oxygen-containing reactant and the third reactant are chemically adsorbed or physically adsorbed without adsorbing the reactants forming the thin film, using nitrogen gas or The inert gas is removed to the reaction chamber. The above two cycles: the process sequence of the first cycle and the second cycle can be replaced, and the number of times of the first cycle and the second cycle of the step is not limited.

The transparent conductive film prepared by the ALD process of the invention can be applied to a solar cell Electrodes and electrical conductors of electronic components, such as tandem conductive lines between solar cells and interlayer electrical conductive films of stacked upper and lower cells in tandem solar cells. The tandem solar cell element is formed by stacking a top cell and a bottom cell. Generally, the upper and lower cells of the thin film solar cell are respectively microcrystalline silicon and amorphous germanium film. (amorphous silicon), the combined structure is generally a cell with a wide energy gap for the incident light first; the transparent conductive layer of the two battery interlayer can be prepared by an ALD process for connecting the upper and lower cells. The conductive film layer has good coating uniformity, precise coating layer number, thickness and precise composition control ability under the ALD process. Controlling the film layer can increase the reflection of light at a suitable number of layers and thickness, can reduce the thickness of the amorphous silicon film, reduce the severity of the light decay phenomenon, and help to improve the overall light energy conversion of the stacked solar cell. Efficiency and stability.

In the method for producing a transparent metal oxide conductive film of the present invention, a method of implementing ZZO (ZnO: ZrO ₂ ) is taken as an example, and reference is made to FIGS. 1A to 1H and 2 . The first reactant, the second reactant, the third reactant, and the fourth reactant for producing the ZZO include H ₂ O ₂ , H ₂ O, O ₂ , O ₂ plasma, O ₃ or plasma O ₃ And one of a metal halide, a metal alkane compound, an alkyl metal halide, a metal acetoacetone compound, a metal alkyl nitride, and the above-mentioned metal group consisting of zinc, zirconium or a combination thereof .

A substrate 111 such as glass is first placed in the reaction chamber 201, and then the reaction chamber is evacuated to a pressure of about 0.1 Torr. The substrate 111 is heated to 50 to 500 ° C, and this embodiment is heated to 180 ° C, and then a gas stream of 20 sccm of diethylzinc (DEZ) in a nitrogen (N ₂ ) delivery gas (first reaction) The gas stream 112 was introduced into the reaction chamber 201 for 0.06 seconds (see Figure 1A for details). During this period, the first portion of the DEZ is chemically adsorbed on the surface of the substrate 111 and forms the chemisorption layer 121. The second portion of the DEZ molecule is adsorbed and loosely fixed to the chemisorbed layer of the substrate 111. The reaction chamber 201 was then washed with N _{2 for} 5 seconds. In such a purge step, the non-chemically adsorbed portion of DEZ is removed from reaction chamber 201 leaving the chemical adsorption layer 121 of DEZ on substrate 111 (see Figure 1B for details).

Next, a 20 sccm N ₂ gas stream (second reactant gas stream) 131 containing H ₂ O was introduced into the reaction chamber 201 for 0.03 seconds while maintaining a pressure of 0.5 Torr and a substrate temperature of 180 ° C. The first portion of the H ₂ O vapor is chemically adsorbed with the chemisorbed layer 121 on the substrate (see Figure 1C for details) to form a film layer of ZnO (see Figure 1D for details). The second part of the H ₂ O molecule adheres and is loosely fixed to the chemical adsorption layer of Zn. It was then washed with N _{2 for} 5 seconds. In the purging step, the non-chemically adsorbed portion of H ₂ O is removed from the reaction chamber 201, and the chemical adsorption layer (first atomic layer film) 141 leaving oxygen (O) is intact in the substrate. 111 (see Figure 1D for details).

Next, a 20 sccm N ₂ gas stream (third reactant gas stream) 151 containing [(CH ₃ ) ₂ N] ₄ Zr (Tetrakisdimhylaminozirconium) was introduced into the reaction chamber 201 for 0.6 seconds while maintaining a pressure of 0.5 Torr and 180 The substrate temperature of °C. The first part of [(CH ₃ ) ₂ N] ₄ Zr reacts with the chemical adsorption layer 141 on the substrate 111 by surface chemisorption (see FIG. 1E for details), and generates Zr in ZZO (ZnO: ZrO ₂ ) (detailed) See Figure 1F). The [(CH ₃ ) ₂ N] ₄ Zr molecule adheres and is loosely fixed to the chemisorption layer 141 of ZnO. Then, it was washed with N _{2 for} 5 seconds. In the purification step, the non-chemically adsorbed portion of [(CH ₃ ) ₂ N] ₄ Zr was removed from the reaction chamber 201, leaving [(CH ₃ ) ₂ The chemical adsorption layer 161 of N] ₂ Zr is intact on the substrate 111 (see Fig. 1F for details).

Next, a 20 sccm N ₂ gas stream (fourth reactant gas stream) 171 containing H ₂ O was introduced into the reaction chamber 201 for 0.03 seconds while maintaining a pressure of 0.5 Torr and a substrate temperature of 180 ° C. The first portion of the H ₂ O vapor is chemically adsorbed with the chemisorbed layer 161 on the substrate (see Figure 1G for details) to form a ZrO ₂ film layer of ZZO. The second portion of the H ₂ O molecule adheres and is loosely fixed to the chemisorption layer 161. Then, it is washed with N _{2 for} 5 seconds. In the cleaning step, the non-chemically adsorbed portion of H ₂ O is removed from the reaction chamber 201, leaving a chemical adsorption layer of oxygen (second atomic layer film) 181 The first atomic layer film 141 is intact (see Figure 1H for details).

Fig. 2 is a schematic view showing a film manufacturing apparatus used in the film manufacturing method according to the present invention. The foregoing specific embodiments will now be described with reference to the flowcharts of Figs. 2 and 3. First, in step S12, a transparent conductive film is formed; after the substrate 111 (for example, a glass substrate) is loaded into the reaction chamber 201, the reaction chamber 201 is brought to a pressure of about 0.1 Torr, and the heater 203 is used. A temperature of about 180 ° C is reached. Further, in step S14 and step S16, the first reactant gas stream 112 containing DEZ is injected into the reaction chamber 201 for 0.06 seconds while maintaining the substrate at 180 ° C and about 0.5 Torr. 20 sccm of N _{2 is} mixed with first reactant 210 (DEZ gas) in first reactant material supply 209 via gas source 218 to form first reactant gas stream 112. As described above, then N ₂ gas and DEZ via a first gas line 204 and the showerhead 202 the mixed stream into the reaction chamber 201 to about 0.06 seconds time. Then the reaction chamber 208 of the pump 201 DEZ unreacted N ₂ gas line 217 to injection of pure N ₂ washing five seconds.

Step S18 and step S20 are continued, and then the second reactant gas stream 131 is injected into the reaction chamber 201 by mixing with 20 sccm of N ₂ and H ₂ O gas for about 0.03 seconds. In this step, the substrate 111 was maintained at 180 ° C and the pressure in the reaction chamber 201 was maintained at about 0.5 Torr. 20 sccm of N _{2 is} mixed with a second reactant 214 (H ₂ O gas) in the second reactant material supply 213 via gas source 218 to form a second reactant gas stream 131, which in turn is passed through gas line 206 and showerhead 202 The mixed H ₂ O and N ₂ gas streams were injected into the reaction chamber 201 for about 0.03 seconds.

The first portion of H ₂ O in the second reactant gas stream 131 is chemically adsorbed to the Zn reaction on the substrate 111 to form a layer of ZnO. When a film of ZnO is formed on the substrate 111, the second portion of the H ₂ O in the second reactant gas stream 131 is loosely fixed to the Zn layer (unreacted H ₂ O). Then the reaction chamber 208 of the pump 201 with N ₂ gas injection line 217 pure N ₂ washing five seconds, or may use an inert gas washing removed.

Then, in step S21, it is determined whether the number of layers and the thickness of the first atomic layer film 141 meet the requirements. If not, step S14 to step S20 (first cycle) may be repeated. If the requirements are met, step S22 and subsequent implementation steps are continued.

Step S22 and step S24 are continued, after the unreacted H ₂ O is cleaned from the reaction chamber 201, the third reactant gas stream 151 containing [(CH ₃ ) ₂ N] ₄ Zr is injected into the reaction chamber 201 for 0.6 seconds. While maintaining the substrate at 180 ° C and about 0.5 Torr. The gas source 218 via 20sccm of N ₂ gas and the third reactant materials to provide a third reaction mixture at 211 was _{212 ([(CH 3) 2} N] 4 Zr gas), a third reactant gas stream 151 is formed. As previously described, the mixed [(CH ₃ ) ₂ N] ₄ Zr and N ₂ gas streams are then injected into the reaction chamber 201 via the third gas line 205 and the showerhead 202 for a period of about 0.6 seconds. Next, the unreacted [(CH ₃ ) ₂ N] ₄ Zr in the reaction chamber 201 was injected into the pure N ₂ purge by the N ₂ gas line 217 for 5 seconds using the pump 208.

Next, step S26 and step S28 are performed, and then the fourth reactant gas stream 171 is injected into the reaction chamber 201 by mixing with 20 sccm of N ₂ and H ₂ O gas for about 0.03 seconds. In this step, the substrate 111 was maintained at 180 ° C and the pressure in the reaction chamber 201 was maintained at about 0.5 Torr. 20 sccm of N _{2 is} mixed with a fourth reactant 216 (H ₂ O gas) in the fourth reactant material supply 215 via gas source 218 to form a fourth reactant gas stream 171, which is then passed via gas line 207 and showerhead 202 The mixed H ₂ O and N ₂ gas streams were injected into the reaction chamber 201 for about 0.03 seconds. H ₂ O The reaction of the first portion 171 of the fourth gas stream react with the adsorbed on the substrate 111 of Zr, generating layer ZrO _2. When a film of ZrO ₂ is formed on the substrate, the second portion of the H ₂ O in the fourth reactant gas stream is loosely immobilized on the Zr layer (unreacted H ₂ O). The reaction chamber 201 is then pumped into the pure N ₂ purge with the N ₂ gas line 217 for 5 seconds using a pump 208, or may be removed by purging with an inert gas.

Then, in step S30, it is determined whether the number and thickness of the transparent conductive film of the ZZO meet the requirements. If not, the steps S14 to S20 (first cycle) or steps S22 to S28 (second cycle) may be repeated. A transparent conductive film having various structures, such as a plurality of layers of the first atomic layer film 141, a transparent conductive film of the second atomic layer film 181, and a plurality of layers of the first atomic layer film 141 are combined with the second atomic layer of the plurality of layers. The transparent conductive film of the film 181, such as a layer of the first atomic layer film 141, is multi-layered The transparent conductive film of the second atomic layer film 181, or any number of the first atomic layer film 141 and the second atomic layer film 181 are alternately arranged to form a transparent conductive film. If so, the process proceeds to step S32 and step S34, and the entire process is terminated with the reaction chamber at room temperature and 1 atm.

In order to improve the film formation quality and film formation speed, it can be plasma-assisted or photo-assisted by using DEZ, [(CH ₃ ) ₂ N] ₄ Zr and H ₂ O, H ₂ O ₂ , O ₂ , O ₃ (for ultraviolet light, infrared light, far red light), or annealing (annealing) to improve film quality and electrical performance. The above-mentioned plasma method, illumination assisting method and heating method of the reactant material supply are not shown in the drawings, but can be implemented by the improvement of the apparatus in Fig. 2, wherein the light used in the illumination mode is ultraviolet light, Infrared or far infrared. The results of the film properties obtained by the practice of the present invention are shown in the list of FIG. 4, and there are three kinds of transparent conductive films proposed in FIG. 4, and the first transparent conductive film is first implemented in S14 to S20 (first cycle). After that, S22 to step S28 (second cycle) are carried out once, and then cyclically repeated to form a ZZO transparent conductive film. The second transparent conductive film is subjected to S14 to S20 (first cycle) for a total of 19 times, and then S22 to S28 (second cycle) is performed once, and then cyclically repeated to form a ZZO transparent conductive film. The third transparent conductive film is subjected to S14 to S20 (first cycle) for a total of 32 times, and then S22 to S28 (second cycle) is performed once, and then cyclically repeated to form a ZZO transparent conductive film.

In the present invention, when the transparent conductive film is formed, the number of times of the first cycle and the second cycle is not limited, and can be produced according to actual needs. Further, the transparent conductive film of the present invention may be formed by interleaving the first cycle and the second cycle. These implementations should all be protected by patents.

Another embodiment of the present invention forms indium gallium oxide IGO (In ₂ O ₃ :Ga ₂ O ₃ ) by atomic layer deposition, and IGO is another transparent conductive film. This embodiment differs from the previous embodiment in that The composition of the first reactant, the second reactant, the third reactant, and the fourth reactant in the production of IGO. The first reactant, the second reactant, the third reactant, and the fourth reactant for producing the IGO include one of H ₂ O ₂ , H ₂ O, O ₂ , O ₂ plasma, O ₃ or plasma O ₃ . And one of a metal halide, a metal alkane compound, an alkyl metal halide, a metal acetoacetone compound, a metal alkyl nitride, and the above-mentioned metal is indium, gallium or a combination thereof.

The transparent metal oxide conductive film of the present invention can be widely applied to an electrical conductor of an electronic component in a solar cell, such as an interlayer electrically conductive film of a stack of upper and lower cells in a tandem solar cell. Referring to the component numbers 51 and 52 of FIG. 5, respectively, a double-junction solar cell element 51 and a triple-junction tandem solar cell element 52, wherein the double junction solar energy In the battery element 51, the component number 511 is a top cell of the component, such as an amorphous silicon film, and the component number 512 is a bottom cell such as a microcrystalline silicon film. , can be separately prepared by PECVD deposition method with different process parameters; and the component number 513 is an interlayer 513 connecting the upper and lower cells of the solar cell element, and the film layer (intermediate layer 513) can be described by the prior implementation method. ALD technology is used to deposit the indium gallium oxide IGO (In ₂ O ₃ :Ga ₂ O ₃ ) or zinc zirconium ZOO (ZnO:ZrO ₂ ) transparent conductive film, which has excellent film coverage and mild process. The original film is damaged to affect the component performance; the component number 514 and the component number 515 are respectively connected to the upper battery and the lower battery and the external circuit to the upper electrode 514 and the lower electrode 515; at least one of the upper electrode 514 or the lower electrode 515 For the transparent conductive film, as the incident surface of the light, the process can be prepared by physical or chemical vapor deposition, or the above ALD technology can be used for indium gallium oxide IGO (In ₂ O ₃ :Ga ₂ O ₃ ) Or deposition of a zinc oxide zirconium ZZO (ZnO: ZrO ₂ ) transparent conductive film. Also in the three-junction stacked solar cell element 52, the elements are stacked by three battery cells 511, 512, 521 designed to absorb different wavelengths and having different energy gaps, wherein the component number 522 is to connect the solar cells. An interlayer 522, which may be indium gallium oxide IGO (In ₂ O ₃ :Ga ₂ O ₃ ) or zinc zirconium zirconium ZOO by ALD technique, as described in the previous embodiment. ZnO:ZrO ₂ ) deposition of a transparent conductive film, and the electrode 514 and the electrode 515 of the upper battery and the lower battery connected to the external circuit can also perform indium gallium oxide IGO (In ₂ O ₃ :Ga ₂ O ₃ ) by the above ALD technique. Or deposition of a zinc oxide zirconium ZZO (ZnO: ZrO ₂ ) transparent conductive film.

The transparent metal oxide conductive film of the invention can be widely applied to electrodes and electrical conductors of electronic components of solar cells, such as conductive films in which solar cells are connected in series in a solar module. . In Fig. 6, the component number 53 is a tandem solar cell element composed of three solar cells, and the component number 531 is a conductive film as an electrode, which can be oxidized by ALD technique as described in the prior embodiment. Deposition of indium gallium IGO (In ₂ O ₃ :Ga ₂ O ₃ ) or zinc zirconium zirconium ZOO (Zno:ZrO ₂ ) transparent conductive film. The component number 532 is an individual single solar cell, and the component process can be prepared by various methods such as physical or chemical vapor deposition or solvent coating; and the component number 533 is a tandem conductor between solar cells. The film layer can also be deposited by using the above ALD technique as a film of indium gallium oxide IGO (In ₂ O ₃ :Ga ₂ O ₃ ) or a zinc zirconium zirconium ZOO (ZnO:ZrO ₂ ) film as a conductive film bonded to other elements. The deposition of indium gallium oxide IGO (In ₂ O ₃ :Ga ₂ O ₃ ) or zinc zirconium ZOO (ZnO:ZrO ₂ ) transparent conductive film is performed by ALD technology, and the film has good coverage and mild process. It will damage the original film. For the formation of the solar cell module, the deposited film can be patterned by using techniques such as lithography etching, mechanical scraping or laser scratching to form an electrically conductive string between adjacent solar cells. even.

111‧‧‧Substrate

112‧‧‧First reactant gas flow

121‧‧‧film layer of the first reactant (chemical adsorption layer)

131‧‧‧Second reactant gas flow

141‧‧‧ Thin film layer of the second reactant (chemical adsorption layer / first atomic layer film)

151‧‧‧ Third reactant gas flow

161‧‧‧film layer of the third reactant (chemical adsorption layer)

171‧‧‧ fourth reactant gas flow

181‧‧‧film layer of the fourth reactant (chemical adsorption layer / second atomic layer film)

201‧‧‧Reaction room

202‧‧‧ shower head

203‧‧‧heater

204‧‧‧First gas pipeline

205‧‧‧ third reactant pipeline

206‧‧‧Second reactant pipeline

207‧‧‧ fourth reactant pipeline

208‧‧‧ pump

209‧‧‧ First Reagent Materials Supply Office

210‧‧‧First reactant

211‧‧‧ Third Reactant Materials Supply Office

212‧‧‧ Third reactant

213‧‧‧Second reactant material supply office

214‧‧‧Second reactant

215‧‧‧ Fourth Reagent Materials Supply Office

216‧‧‧ fourth reactant

217‧‧‧N ₂ gas or inert gas pipeline

218‧‧‧N ₂ gas or inert gas source

51‧‧‧Double junction stacked solar cell composite components

511‧‧‧Upper battery

512‧‧‧Battery cell

513‧‧‧Transparent conductive film formed by ALD

514‧‧‧Upper electrode

515‧‧‧ lower electrode

52‧‧‧Three junction stacked solar cell composite components

521‧‧‧ Middle cell (middle cell)

53‧‧‧Solar cells in series (ie solar cell modules)

531‧‧‧Transparent conductive film formed by ALD

532‧‧‧Solar cell unit

533‧‧‧Electrical film in series with adjacent battery cells

1A to 1H illustrate steps of a method of forming a thin film using atomic layer deposition according to a specific embodiment of the present invention.

Fig. 2 is a schematic view showing a manufacturing apparatus used in the method for producing a film according to the present invention.

Fig. 3 is a flow chart showing the method of producing a film according to the present invention.

Fig. 4 is a graph showing the properties of a zinc zirconium oxide ZOO (ZnO:ZrO ₂ ) film obtained by the practice of the present invention.

Fig. 5 and Fig. 6 are electronic components obtained by using the present invention.

Claims (4)

A method for forming a transparent conductive film by atomic layer deposition comprises the steps of: (A) injecting a first reactant into a reaction chamber to react with a substrate, and after reacting, using nitrogen or inert gas to react unreacted The first reactant is removed from the reaction chamber; (B) a second reactant is injected into the reaction chamber to react with the first reactant, and a first atomic layer film is formed on the substrate. After the reaction, The unreacted second reactant is removed from the reaction chamber using nitrogen or inert gas; (C) a third reactant is injected into the reaction chamber, and the third reactant is adsorbed to the first atomic layer On the film, after the reaction, the unreacted third reactant is removed from the reaction chamber using nitrogen or inert gas; (D) injecting a fourth reactant into the reaction chamber to react with the third reactant, Forming a second atomic layer film on the substrate, and after the reaction, removing the unreacted fourth reactant from the reaction chamber using nitrogen or inert gas, and forming the first atomic layer film and the first a transparent conductive film composed of a diatomic layer film; Wherein the first reactant / reaction system of the second _{H 2 O 2, H 2 O} , O 2, O 2 plasma, plasma O _3, or O _3, the second reactant / reaction product of the first a metal halide, a metal alkane compound, a metal halide of an alkyl group, a metal acetoacetone compound, a metal alkyl nitride, one of the above-mentioned metal zinc/zirconium or a combination thereof, a third reactant / the fourth reactant is H ₂ O ₂ , H ₂ O, O ₂ , O ₂ plasma, O ₃ or O ₃ plasma, the fourth reactant / the third reactant metal halide a metal halide, a metal halide of an alkyl group, a metal acetoacetone compound, a metal alkyl nitride, one of the above-mentioned metal zirconium/zinc or a combination thereof, and the transparent conductive The film is zinc zirconium oxide ZOO (ZnO: ZrO ₂ ). The method of claim 1, wherein the zinc zirconium transparent conductive film is used as an intermediate layer electrically conductive film between the cells in the stacked solar cell. A method for forming a transparent conductive film by atomic layer deposition comprises the steps of: (A) injecting a first reactant into a reaction chamber to react with a substrate, and after reacting, using nitrogen or inert gas to react unreacted The first reactant is removed from the reaction chamber; (B) a second reactant is injected into the reaction chamber to react with the first reactant, and a first atomic layer film is formed on the substrate. After the reaction, The unreacted second reactant is removed from the reaction chamber using nitrogen or inert gas; (C) a third reactant is injected into the reaction chamber, and the third reactant is adsorbed to the first atomic layer On the film, after the reaction, the unreacted third reactant is removed from the reaction chamber using nitrogen or inert gas; (D) injecting a fourth reactant into the reaction chamber to react with the third reactant, Forming a second atomic layer film on the substrate, and after the reaction, removing the unreacted fourth reactant from the reaction chamber using nitrogen or inert gas, and forming the first atomic layer film and the first a transparent conductive film composed of a diatomic layer film; Wherein the first reactant / reaction system of the second _{H 2 O 2, H 2 O} , O 2, O 2 plasma, plasma O _3, or O _3, the second reactant / reaction product of the first a metal halide, a metal alkane compound, a metal halide of an alkyl group, a metal acetoacetone compound, a metal alkyl nitride, one of the above-mentioned metal indium/gallium or a combination thereof, a third reactant / the fourth reactant is H ₂ O ₂ , H ₂ O, O ₂ , O ₂ plasma, O ₃ or O ₃ plasma, the fourth reactant / the third reactant metal halide a metal halide, a metal halide of an alkyl group, a metal acetoacetone compound, a metal alkyl nitride, one of the above-mentioned metal-based gallium/indium or a combination thereof, and the transparent conductive The film is indium gallium oxide IGO (In ₂ O ₃ :Ga ₂ O ₃ ). The method of claim 3, wherein the indium gallium oxide transparent conductive film is used as an intermediate layer electrically conductive film between the cells in the stacked solar cell.