CN102569517A - Nano silicon film solar battery elliptic polarized light real-time monitoring preparation method - Google Patents
Nano silicon film solar battery elliptic polarized light real-time monitoring preparation method Download PDFInfo
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Abstract
The invention relates to a nano silicon film solar battery elliptic polarized light real-time monitoring preparation method, which comprises five steps: step 1: anisotropic corrosion on a monocrystalline silicon chip is undertaken by adopting a wet chemistry method to obtain a pyramid-shaped napped silicon chip substrate; step 2: a back electrode of the nano silicon film solar battery is prepared through a heat evaporation method or a magnetron sputtering method; step 3: an I layer nano silicon film is prepared by adopting a plasma enhanced chemical gas-phase deposition method through silane SiH4, an N layer nano silicon film is prepared by introducing the silane SiH4 and phosphorane PH3 mixed gas, and a P layer nano silicon film is prepared by introducing silane SiH4 and borane B2H5 mixed gas; step 4: the growth of the film is instantly monitored by adopting elliptic polarized light during the deposition process of the nano silicon film in step 3; and step 5: a transparent conductive film electrode and a top electrode of the nano silicon film solar battery can be prepared by adopting the heat evaporation method, magnetron sputtering method or the silk screen printing technology. The method has good application prospect in the photoelectric application and novel energy technical field.
Description
(1) technical field:
The present invention relates to a kind of preparation method of thin-film solar cells, relate in particular to the ellipse garden of a kind of thin-film solar cell of nano silicon polarised light and monitor the preparation method in real time, belong to photovoltaic applications and technical field of new energies.
(2) background technology:
Earth's stored such as non-renewable energy resources such as coal and oil amount is limited, and social high speed development needs mass energy.So energy problem becomes the bottleneck of restriction international community economic development day by day, more and more countries comes into effect " sunlight program ", develops the solar power generation resource, seeks the new power of economic development.Solar energy is a kind of inexhaustible, nexhaustible clear energy sources.Applied solar energy neither air pollution can occur, also can not influence the ecological balance, as long as the sunlight place in one's power all can utilize solar energy.
The utilization of solar energy at present mainly contains photo-thermal, photochemistry conversion and three kinds of forms of solar cell generating.The solar thermal utilization cost is low, convenient, efficient is higher, but is unfavorable for power transfer, generally can only use on the spot, and the output form of energy does not have versatility.With photosynthetic form ubiquity, but the mankind can't utilize well at present at occurring in nature for photochemistry conversion.Solar cell is a kind of small-sized semiconductor device, and when sunlight projected it surperficial, it just was directly changed into electric energy to luminous energy.The generating utilization of solar cell as the final form of expression, has the characteristics easily of transmitting with electric energy, has the above two irreplaceable advantages at aspects such as versatility, storabilities.
The technology of preparing of monocrystalline silicon and polycrystalline silicon solar cell is very ripe, and the photoelectric conversion efficiency of its product reaches 17%-22%, accounts for 95% of solar cell produce market share.But high material cost is dominate in whole production costs, makes its cost high all the time, and will consume a lot of energy in the making overall process.For this reason, the second generation solar cell of based thin film technology has just grown up.Film photovoltaic cell technology; Through the years of researches development; Mainly comprise amorphous silicon (a-Si) thin film solar cell and (μ c-Si) microcrystalline silicon solar cell and Nano thin film solar cell, cadmium telluride (CdTe) thin film solar cell and copper indium (gallium) selenium (CI (Ga) Se) thin film solar cell and dye sensitization TiO
2Nano film solar battery.Thin film solar cell is done raw material (＞300 micron thick) without silicon chip, but is depositing a semiconductor active layer of pressing micron to arrive micron dimension on the inexpensive substrate such as glass or on the flexible substrate, and adopts low temperature process deposit film technology.
In numerous hull cells, one of up-and-coming thin film solar cell is the Nano thin film solar cell.This is to be that the component of Nano thin film is that a large amount of tiny crystal grains accounts for total volume percent～50% because Nano thin film has unique microstructure; Other 50% is that silicon atom by disordered state in the middle of the little crystal grain constitutes; Each intergranule interface depth is a 2-4 atomic layer; Compare with polysilicon (pc-Si) with amorphous silicon (a-Si:H), microcrystal silicon (μ c-Si:H), the existence at nano-scale silicon crystal grain and a large amount of interfaces has important effect promptly owing to quantum-mechanical tunnel effect shows high conductivity (δ=10 to the membrane structure rerum natura
-3～10
-1Ω
-1Cm
-1), the low conductivity activation energy (characteristic of Δ E=0.12～0.15eV); And the peak wavelength of its hull cell spectral response curve promptly moves to the shortwave direction than the peak wavelength of monocrystalline silicon is little; This shows that the Nano thin film solar cell is higher than monocrystalline silicon at the visible light and the infra-red range absorption coefficient of light; This helps the abundant absorption of sunlight and improves photoelectric conversion efficiency, and the theoretical value of its photoelectric conversion efficiency is 31.34%, and this is than theoretical value 27% height of single crystal silicon solar cell.The optical energy gap E of Nano thin film
g OptScope be 1.6～2.2eV, different crystalline state ratio X
cHas the optical energy gap E of different in width with the silicon thin film of crystallite dimension d value
g OptValue, and through controlling the structure of the change nc-Si:H film that process conditions in the precipitation process can be artificial, and then to change its optical energy gap be that more little its optical energy gap of contained crystallite dimension is big more in the silicon fiml.Adjusting through technological parameter changes the optical energy gap value of nc-Si:H film like this, just can match out rational top at the bottom of the battery band gap make up.In addition, Nano thin film preparation need not High temperature diffusion technology, and the S-W effect that has overcome the amorphous silicon membrane battery basically is photic efficiency degradation effect, and its preparation technology is that pecvd process and modern semiconductors industry are complementary and can reduce cost.So Nano thin film possibly become the photovoltaic material that replaces monocrystalline silicon, amorphous silicon.
But the maturity of the film preparing technology of above-mentioned all thin-film solar cells is very poor, and this photoelectric conversion efficiency that shows thin-film solar cells is low, and does not have the repeatability of technology.
The present invention is intended to the real-time monitoring technique of ellipse garden polarised light and adopts Nano thin film material preparation film photovoltaic cell, with repeatability that promotes technology and the photoelectric conversion efficiency that improves thin-film solar cell of nano silicon.
(3) summary of the invention
1. goal of the invention:
The purpose of this invention is to provide the ellipse garden of a kind of thin-film solar cell of nano silicon polarised light and monitor the preparation method in real time, it has overcome the deficiency of prior art, adopts the ellipse garden real-time monitoring technique of polarised light to prepare thin-film solar cell of nano silicon; Through the real-time monitoring technique of ellipse garden polarised light, can improve the repeatability of thin-film solar cell of nano silicon technology, and improve the photoelectric conversion efficiency of thin-film solar cell of nano silicon.
2. technical scheme content:
The ellipse garden of a kind of thin-film solar cell of nano silicon of the present invention polarised light is monitored the preparation method in real time, and this method may further comprise the steps:
Step 1: adopt wet chemistry method that monocrystalline silicon piece is carried out anisotropic etch, obtain the matte silicon chip substrate of pyramid shape.
Step 2: adopt thermal evaporation method or magnetically controlled sputter method to prepare the back electrode of thin-film solar cell of nano silicon.
Step 3: adopting the PECVD method is the plasma enhanced chemical vapor deposition method, feeds silane SiH
4Preparation I layer Nano thin film feeds silane SiH
4With phosphine PH
3Prepare N layer Nano thin film Deng mist, feed silane SiH
4With borine B
2H
5Prepare P layer Nano thin film Deng mist.
Step 4: in step 3 depositing nano silicon thin film process, adopt the preparation method of the real-time monitoring film growth course of ellipse garden polarised light, this is the core of present patent application.
Step 5: adopt thermal evaporation method or magnetically controlled sputter method or screen printing technique to prepare the electrically conducting transparent membrane electrode and the top electrode (deleting the utmost point) of thin-film solar cell of nano silicon.
Wherein, The concrete practice of step 1 is: be placed on after silicon chip cleans and use HF in the polytetrafluoroethylcontainer container: the weak solution of deionized water=1: 50 is corroded the 9-11 time in second; Sour in the time about second at 29-31 then with a large amount of deionized water rinsing HF, thus remove the silicon dioxide layer on the monocrystalline silicon piece.Adopt the method for aqueous slkali chemical corrosion promptly to regulate the corrosion rate anisotropy factor as reactant and with isopropyl alcohol as additive with NaOH; The mixed solution of its NaOH and isopropyl alcohol carries out anisotropic etch to monocrystalline silicon; NaOH concentration 3%; The consumption 5% of isopropyl alcohol, 90 ℃ of reaction temperatures, etching time is 50min.Under this condition, the texture surface of preparing pyramid-like is the matte silicon chip substrate.
Wherein, the concrete practice of step 2 is: when adopting thermal evaporation method to prepare back electrode, system's base vacuum is evacuated to 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～400 ℃, and metal conductive films such as thermal resistance evaporation or electron beam evaporation rafifinal Al film all can; When adopting magnetically controlled sputter method to prepare back electrode, system's base vacuum is evacuated to 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～400 ℃, sputtering current 0.4-0.8A, sputtering voltage 350-450V, working gas Ar
2, operating air pressure 0.5-3Pa, metallic targets such as sputter rafifinal Al target, thus on sample surfaces, form metal conductive film such as rafifinal Al film; Carrying out the vacuum annealing processing again is that system's base vacuum is evacuated to 8.0 * 10
-4Below the Pa, annealing temperature is 450 ℃～560 ℃, and annealing time is 5min～20min, and at this moment the aluminium film of deposition is obviously fine and close, and the combining of film and substrate improves, and helps reducing the resistance of film.
Wherein, the concrete practice of step 3 is:: earlier system's base vacuum degree is extracted into 8.0 * 10
-4Below the Pa, feed concentration that hydrogen diluted again and be 5% high purity silane SiH
4, temperature is 200-380 ℃, and operating air pressure is 1.0-3.0Torr, and radio-frequency power is 40-60W, adopts these process conditions can prepare I layer Nano thin film, and its crystalline state content is between (50 ± 5) %, and the crystalline state peak is at 509-518cm
-1Between, room-temperature conductivity reaches 10
1Ω
-1Cm
-1-10
2Ω
-1Cm
-1Cm
-1On the basis of above-mentioned technology, feed high-purity hydrogen H again
2The concentration of having diluted with hydrogen is 0.5% high-purity phosphine PH
3, its silane SiH
4, hydrogen H
2, phosphine PH
3The flow-rate ratio of these three kinds of working gass is 5: 100: 5-15 (SCCM), and adopt these process conditions can prepare N layer Nano thin film, its conductivity reaches 10
1Ω
-1Cm
-1-10
2Ω
-1Cm
-1Cm
-1On the basis of above-mentioned technology, with phosphine PH
3Change borine B into
2H
5Promptly feed high-purity hydrogen H
2The concentration of having diluted with hydrogen is 5% high-purity borine B
2H
5, its silane SiH
4, hydrogen H
2, borine B
2H
5The flow-rate ratio of these three kinds of working gass is 5: 100: 0.3-0.8 (SCCM), and Dc bias is 100-300V, adopts these process conditions can prepare P layer Nano thin film, its conductivity reaches 10
1Ω
-1Cm
-1-10
2Ω
-1Cm
-1
Wherein, the concrete practice of step 4 is: adopt extinction type ellipse garden polarization flash ranging film thickness gauge principle, in the vacuum insulation chamber of work chamber both sides, the polarizer, quarter-wave plate and analyzer, laser are installed respectively; Wavelength 635nm laser is through the polarizer and quarter-wave plate; Again through work chamber's the left window; Get into work chamber and spend oblique incidence in sample surfaces with 60 °-80 °; Its folded light beam gets into right forevacuum chamber through work chamber's right side window, is incident in photomultiplier or optical semiconductor battery and is surveyed its light intensity and change through analyzer again.For the film of setting; Its light intensity was zero when given ellipsometric parameter Δ, Ψ were arranged promptly corresponding to certain polarizer angle and analyzer angle, and in thin film growth process, its light intensity changes has corresponding variation; When light intensity is zero; The film of just growing and setting, shutdown at this moment stops film growth, thereby reaches the purpose of real-time monitoring film growth.
Wherein, the concrete practice of step 5 is: when adopting thermal evaporation method to prepare electrode, and system's base vacuum: 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～500 ℃, and thermal resistance evaporation or electron beam evaporation are even can; When adopting magnetically controlled sputter method to prepare electrode, system's base vacuum: 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～500 ℃, sputtering current 0.4-0.8A, sputtering voltage 350-450V, working gas Ar
2, operating air pressure 0.5-3Pa; Screen printing technique adopts general screen printing technique.When adopting magnetically controlled sputter method to prepare electrically conducting transparent membrane electrode such as ITO, system's base vacuum: 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～500 ℃, feeds high-purity argon gas Ar and high purity oxygen gas O
2, the flow-rate ratio of these two kinds of working gass is 100: 1.5-2.5 (SCCM), operating air pressure 0.5-3Pa; Sputtering current 0.4-0.6A, sputtering voltage 350-420V.It is that ITO or Al-Doped ZnO are AZO etc. that Coating Materials adopts electrically conducting transparent membrane material such as indium tin oxide, and top electrode (deleting the utmost point) material adopts metal film such as aluminium AL film etc. or each metal film composite membrane such as titanium palladium-silver etc.
3. advantage and effect:
Advantage that technology of the present invention compared with prior art has and good effect: adopt the real-time monitoring film growth course of ellipse garden polarised light, thereby improved the repeatability of Nano thin film photovoltaic cell technology; Its optimal spectrum response wave band of the Nano thin film photovoltaic cell that technology of the present invention is prepared is near 900nm; Optimal spectrum response wave band 1000nm than single crystal silicon solar cell has taken place to move to the shortwave direction, thereby is dominant at Nano thin film solar cell aspect the energy that absorbs the visible region; Technology of the present invention is to adopt silane as working gas, thereby is the low-cost method for preparing the silicon thin film photovoltaic cell.
(4) description of drawings:
Fig. 1 is a process chart of the present invention.
Symbol description is following among the figure:
1, sample cleans and making herbs into wool
2, system back electrode and annealing in process
3, ellipse garden polarised light is monitored in real time
4, system I layer, N layer, P layer Nano thin film
5, system electrically conducting transparent membrane electrode and top electrode (deleting the utmost point)
(5) embodiment:
See also Fig. 1, the ellipse garden of a kind of thin-film solar cell of nano silicon of the present invention polarised light is monitored the preparation method in real time, and it is following to enumerate specific embodiment:
Embodiment one
See Fig. 1, the ellipse garden of a kind of thin-film solar cell of nano silicon of the present invention polarised light is monitored the preparation method in real time, may further comprise the steps:
Step 1: adopting conventional silicon chip cleaning is after improved RCA cleaning is cleaned P type silicon chip; Be placed on and use HF in the polytetrafluoroethylcontainer container: deionized water=weak solution of 1: 50 is corroded the time in 10 seconds; Sour with a large amount of deionized water rinsing HF in 30 seconds then, thus remove the silicon dioxide layer on the monocrystalline silicon piece.Adopt the method for aqueous slkali chemical corrosion promptly to regulate the corrosion rate anisotropy factor as reactant and with isopropyl alcohol as additive with NaOH; The mixed solution of its NaOH and isopropyl alcohol carries out anisotropic etch to monocrystalline silicon; NaOH concentration 3%; The consumption 5% of isopropyl alcohol, 90 ℃ of reaction temperatures, etching time is 50min.Under this condition, prepare the texture surface of pyramid-like.
Step 2: the magnetic control sputtering system base vacuum taken out end 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃, sputtering current 0.8A, sputtering voltage 350V, working gas Ar
2, operating air pressure 0.5Pa, metallic targets such as sputter rafifinal Al target, thus on sample surfaces, form metal conductive film such as rafifinal Al film; Carrying out that vacuum annealing handles is that system's base vacuum is taken out and ended 8.0 * 10 again
-4Below the Pa, annealing temperature is 560 ℃, and annealing time is 20min, and at this moment the aluminium film of deposition is obviously fine and close, and the combining of film and substrate improves, and helps reducing the resistance of film.
Step 3: plasma enhanced chemical vapor deposition (PECVD) system base vacuum degree is extracted into 8.0 * 10
-4Below the Pa, feed concentration that hydrogen diluted again and be 5% high purity silane SiH
4, temperature is 220 ℃, and operating air pressure is 3.0Torr, and radio-frequency power is 60W, adopts these process conditions and can prepare I layer Nano thin film under the monitoring in real time at ellipse garden polarised light.Import sample into another in plasma enhanced chemical vapor deposition (PECVD) system again, this plasma enhanced chemical vapor deposition (PECVD) system base vacuum degree is extracted into 8.0 * 10
-4Below the Pa, feed high-purity hydrogen H again
2The concentration of having diluted with hydrogen is 0.5% high-purity phosphine PH
3, its silane SiH
4, hydrogen H
2, phosphine PH
3The flow-rate ratio of these three kinds of working gass is 5: 100: 7 (SCCM), adopts these process conditions and can prepare N layer Nano thin film under the monitoring in real time at ellipse garden polarised light.
Step 4: at above-mentioned depositing nano silicon thin film is in the process of step 3; Open helium neon laser; Wavelength 635nm laser, gets into work chamber and spends oblique incidence in sample surfaces with 70 ° again through work chamber's the left window through the polarizer and quarter-wave plate; Its folded light beam gets into right forevacuum chamber through work chamber's right side window, is incident in photomultiplier or optical semiconductor battery and is surveyed its light intensity and change through analyzer again.For the film of setting; Its light intensity was zero when given ellipsometric parameter Δ, Ψ were arranged promptly corresponding to certain polarizer angle and analyzer angle; In thin film growth process, its light intensity changes has corresponding variation, when light intensity is zero; The film of just growing and setting, shutdown at this moment stops film growth.
Step 5: adopt magnetically controlled sputter method to prepare ITO electrically conducting transparent membrane electrode.The magnetic control sputtering system base vacuum taken out end 8.0 * 10
-4Below the Pa, sample temperature is 230 ℃, feeds high-purity argon gas Ar and high purity oxygen gas O
2, the flow-rate ratio of these two kinds of working gass is 100: 1.5 (SCCM), operating air pressure 0.8Pa; Sputtering current 0.5, sputtering voltage 400V, thus on Nano thin film photovoltaic cell surface, plated the layer of transparent conducting film, play passivation and the effect of electrically conducting transparent membrane electrode.The top electrode that adopts thermal evaporation method to prepare thin-film solar cell of nano silicon again is grid (contains collector and conflux the utmost point etc.).Evaporation coating system base vacuum is evacuated to 8.0 * 10
-4Below the Pa, sample temperature is 230 ℃, carries out thermal resistance evaporation, vaporization voltage 20V, evaporation current 40A, evaporation time 2min.
Embodiment two
See Fig. 1, the ellipse garden of a kind of thin-film solar cell of nano silicon of the present invention polarised light is monitored the preparation method in real time, may further comprise the steps:
Step 1: adopting conventional silicon chip cleaning is after improved RCA cleaning is cleaned N type silicon chip; Be placed on and use HF in the polytetrafluoroethylcontainer container: the weak solution of deionized water=1: 50 corrode 10 seconds then in 30 seconds with a large amount of deionized water rinsing HF acid, thereby remove the silicon dioxide layer on the monocrystalline silicon piece.Adopt the method for aqueous slkali chemical corrosion promptly to regulate the corrosion rate anisotropy factor as reactant and with isopropyl alcohol as additive with NaOH; The mixed solution of its NaOH and isopropyl alcohol carries out anisotropic etch to monocrystalline silicon; NaOH concentration 3%; The consumption 5% of isopropyl alcohol, 95 ℃ of reaction temperatures, etching time is 50min.Under this condition, prepare the texture surface of pyramid-like.
Step 2: the magnetic control sputtering system base vacuum is evacuated to 8.0 * 10
-4Below the Pa, sample temperature is 260 ℃, sputtering current 0.9A, sputtering voltage 350V, working gas Ar
2, operating air pressure 0.6Pa, metallic targets such as sputter rafifinal Al target, thus on sample surfaces, form metal conductive film such as rafifinal Al film; Carrying out the vacuum annealing processing again is that system's base vacuum is evacuated to 8.0 * 10
-4Below the Pa, annealing temperature is 560 ℃, and annealing time is 25min, and at this moment the aluminium film of deposition is obviously fine and close, and the combining of film and substrate improves, and helps reducing the resistance of film.
Step 3: plasma enhanced chemical vapor deposition (PECVD) system base vacuum degree is extracted into 8.0 * 10
-4Below the Pa, feed concentration that hydrogen diluted again and be 5% high purity silane SiH
4, temperature is 210 ℃, and operating air pressure is 2.0Torr, and radio-frequency power is 50W, adopts these process conditions and can prepare I layer Nano thin film under the monitoring in real time at ellipse garden polarised light.Import sample into another in plasma enhanced chemical vapor deposition (PECVD) system again, this plasma enhanced chemical vapor deposition (PECVD) system base vacuum degree is extracted into 8.0 * 10
-4Below the Pa, feed high-purity hydrogen H
2The concentration of having diluted with hydrogen is 5% high-purity borine B
2H
5, its silane SiH
4, hydrogen H
2, borine B
2H
5The flow-rate ratio of these three kinds of working gass is 5: 100: 0.4 (SCCM), and Dc bias is 200V, and temperature is 210 ℃, and operating air pressure is 2.0Torr, and radio-frequency power is 50W, adopts these process conditions can prepare P layer Nano thin film.
Step 4: at above-mentioned depositing nano silicon thin film is in the step 3 process; Open helium neon laser; Wavelength 635nm laser, gets into work chamber and spends oblique incidence in sample surfaces with 70 ° again through work chamber's the left window through the polarizer and quarter-wave plate; Its folded light beam gets into right forevacuum chamber through work chamber's right side window, is incident in photomultiplier or optical semiconductor battery and is surveyed its light intensity and change through analyzer again.For the film of setting; Its light intensity was zero when given ellipsometric parameter Δ, Ψ were arranged promptly corresponding to certain polarizer angle and analyzer angle; In thin film growth process, its light intensity changes has corresponding variation, when light intensity is zero; The film of just growing and setting, shutdown at this moment stops film growth.
Step 5: adopt magnetically controlled sputter method to prepare ITO electrically conducting transparent membrane electrode.The magnetic control sputtering system base vacuum is evacuated to 8.0 * 10
-4Below the Pa, sample temperature is 220 ℃, feeds high-purity argon gas Ar and high purity oxygen gas O
2, the flow-rate ratio of these two kinds of working gass is 100: 1.5 (SCCM), operating air pressure 1.0Pa; Sputtering current 0.8, sputtering voltage 400V, thus on Nano thin film photovoltaic cell surface, plated the layer of transparent conducting film, play passivation and the effect of electrically conducting transparent membrane electrode.The top electrode that adopts thermal evaporation method to prepare thin-film solar cell of nano silicon again is grid (contains collector and conflux the utmost point etc.).Evaporation coating system base vacuum is evacuated to 8.0 * 10
-4Below the Pa, sample temperature is 230 ℃, carries out thermal resistance evaporation, vaporization voltage 15V, evaporation current 70A, evaporation time 2min.
Embodiment three
See Fig. 1, the ellipse garden of a kind of thin-film solar cell of nano silicon of the present invention polarised light is monitored the preparation method in real time, may further comprise the steps:
Step 1: adopting conventional silicon chip cleaning is after improved RCA cleaning is cleaned P type silicon chip; Be placed on and use HF in the polytetrafluoroethylcontainer container: the weak solution of deionized water=1: 50 corrode 10 seconds then in 30 seconds with a large amount of deionized water rinsing HF acid, thereby remove the silicon dioxide layer on the monocrystalline silicon piece.Adopt the method for aqueous slkali chemical corrosion promptly to regulate the corrosion rate anisotropy factor as reactant and with isopropyl alcohol as additive with NaOH; The mixed solution of its NaOH and isopropyl alcohol carries out anisotropic etch to monocrystalline silicon; NaOH concentration 3%; The consumption 5% of isopropyl alcohol, 85 ℃ of reaction temperatures, etching time is 60min.Under this condition, prepare the texture surface of pyramid-like.
Step 2: the magnetic control sputtering system base vacuum is evacuated to 9.0 * 10
-4Below the Pa, sample temperature is 200 ℃, sputtering current 1.1A, sputtering voltage 350V, working gas Ar
2, operating air pressure 1.2Pa, metallic targets such as sputter rafifinal Al target, thus on sample surfaces, form metal conductive film such as rafifinal Al film; Carrying out the vacuum annealing processing again is that system's base vacuum is evacuated to 8.0 * 10
-4Below the Pa, annealing temperature is 570 ℃, and annealing time is 15min, and at this moment the aluminium film of deposition is obviously fine and close, and the combining of film and substrate improves, and helps reducing the resistance of film.
Step 3: plasma enhanced chemical vapor deposition (PECVD) system base vacuum degree is extracted into 8.0 * 10
-4Below the Pa, feed concentration that hydrogen diluted again and be 5% high purity silane SiH
4, temperature is 200 ℃, and operating air pressure is 2.0Torr, and radio-frequency power is 40W, adopts these process conditions and can prepare I layer Nano thin film under the monitoring in real time at ellipse garden polarised light.Import sample into another in plasma enhanced chemical vapor deposition (PECVD) system again, this plasma enhanced chemical vapor deposition (PECVD) system base vacuum degree is extracted into 9.0 * 10
-4Below the Pa, feed high-purity hydrogen H again
2The concentration of having diluted with hydrogen is 0.5% high-purity phosphine PH
3, its silane SiH
4, hydrogen H
2, phosphine PH
3The flow-rate ratio of these three kinds of working gass is 5: 100: 8 (SCCM), and temperature is 200 ℃, and operating air pressure is 2.0Torr, and radio-frequency power is 40W, adopts these process conditions and can prepare N layer Nano thin film under the monitoring in real time at ellipse garden polarised light.
Step 4: at above-mentioned depositing nano silicon thin film is in the process of step 3; Open helium neon laser; Wavelength 635nm laser, gets into work chamber and spends oblique incidence in sample surfaces with 70 ° again through work chamber's the left window through the polarizer and quarter-wave plate; Its folded light beam gets into right forevacuum chamber through work chamber's right side window, is incident in photomultiplier or optical semiconductor battery and is surveyed its light intensity and change through analyzer again.For the film of setting; Its light intensity was zero when given ellipsometric parameter Δ, Ψ were arranged promptly corresponding to certain polarizer angle and analyzer angle; In thin film growth process, its light intensity changes has corresponding variation, when light intensity is zero; The film of just growing and setting, shutdown at this moment stops film growth.
Step 5: adopt magnetically controlled sputter method to prepare ITO electrically conducting transparent membrane electrode.The magnetic control sputtering system base vacuum is evacuated to 9.0 * 10
-4Below the Pa, sample temperature is 230 ℃, feeds high-purity argon gas Ar and high purity oxygen gas O
2, the flow-rate ratio of these two kinds of working gass is 100: 1.5 (SCCM), operating air pressure 0.8Pa; Sputtering current 0.7, sputtering voltage 380V, thus on Nano thin film photovoltaic cell surface, plated the layer of transparent conducting film, play passivation and the effect of electrically conducting transparent membrane electrode.The top electrode that adopts screen printing technique to prepare thin-film solar cell of nano silicon again is grid (contains collector and conflux the utmost point etc.).
The above is merely preferred embodiment of the present invention, and the equalization design of doing according to claim of the present invention such as becomes, and all should be technical scheme of the present invention and contains.Like substrate is glass and stainless steel substrates etc., all should be technical scheme of the present invention and contains.
In sum; The invention provides the ellipse garden of a kind of Nano thin film photovoltaic cell polarised light and monitor the preparation method in real time; Through the real-time monitoring technique of ellipse garden polarised light, can improve the repeatability of Nano thin film photovoltaic cell technology, and improve the photoelectric conversion efficiency of thin-film solar cell of nano silicon.Film photovoltaic cell preparation method's of the present invention cost is low, and good reproducibility can be applicable.Therefore, patent application is proposed in accordance with the law.
Claims (6)
1. the ellipse garden of a thin-film solar cell of nano silicon polarised light is monitored the preparation method in real time, and it is characterized in that: this method may further comprise the steps:
Step 1: adopt wet chemistry method that monocrystalline silicon piece is carried out anisotropic etch, obtain the matte silicon chip substrate of pyramid shape;
Step 2: adopt thermal evaporation method or magnetically controlled sputter method to prepare the back electrode of thin-film solar cell of nano silicon;
Step 3: adopting the PECVD method is the plasma enhanced chemical vapor deposition method, feeds silane SiH
4Preparation I layer Nano thin film feeds silane SiH
4With phosphine PH
3Mist prepares N layer Nano thin film, feeds silane SiH
4With borine B
2H
5Mist prepares P layer Nano thin film;
Step 4: in step 3 depositing nano silicon thin film process, adopt the process of the real-time monitoring film growth of ellipse garden polarised light;
Step 5: the electrically conducting transparent membrane electrode and the top electrode that adopt thermal evaporation method or magnetically controlled sputter method or screen printing technique to prepare thin-film solar cell of nano silicon are promptly deleted the utmost point.
2. the ellipse garden of a kind of thin-film solar cell of nano silicon according to claim 1 polarised light is monitored the preparation method in real time; It is characterized in that: the concrete practice of step 1 is: be placed on after silicon chip cleans and use HF in the polytetrafluoroethylcontainer container: the weak solution of deionized water=1: 50 is corroded the 9-11 time in second; Sour in the time of second at 29-31 then with a large amount of deionized water rinsing HF, thus remove the silicon dioxide layer on the monocrystalline silicon piece; Adopt the method for aqueous slkali chemical corrosion promptly to regulate the corrosion rate anisotropy factor as reactant and with isopropyl alcohol as additive with NaOH; The mixed solution of its NaOH and isopropyl alcohol carries out anisotropic etch to monocrystalline silicon; NaOH concentration 3%; The consumption 5% of isopropyl alcohol, 90 ℃ of reaction temperatures, etching time is 50min; Under this condition, the texture surface of preparing pyramid-like is the matte silicon chip substrate.
3. the ellipse garden of a kind of thin-film solar cell of nano silicon according to claim 1 polarised light is monitored the preparation method in real time, and it is characterized in that: the concrete practice of step 2 is: when adopting thermal evaporation method to prepare back electrode, system's base vacuum is evacuated to 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～400 ℃, and thermal resistance evaporation or electron beam evaporation rafifinal Al metal conductive film all can be used; When adopting magnetically controlled sputter method to prepare back electrode, system's base vacuum is evacuated to 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～400 ℃, sputtering current 0.4-0.8A, sputtering voltage 350-450V, working gas Ar
2, operating air pressure 0.5-3Pa, sputter rafifinal Al target is made metallic target, is metal conductive film thereby on sample surfaces, form rafifinal Al film; Carrying out the vacuum annealing processing again is that system's base vacuum is evacuated to 8.0 * 10
-4Below the Pa, annealing temperature is 450 ℃～560 ℃, and annealing time is 5min～20min, and at this moment the aluminium film of deposition is obviously fine and close, and the combining of film and substrate improves, and helps reducing the resistance of film.
4. the ellipse garden of a kind of thin-film solar cell of nano silicon according to claim 1 polarised light is monitored the preparation method in real time, and it is characterized in that: the concrete practice of step 3 is: earlier system's base vacuum degree is extracted into 8.0 * 10
-4Below the Pa, feed concentration that hydrogen diluted again and be 5% high purity silane SiH
4, temperature is 200-380 ℃, and operating air pressure is 1.0-3.0Torr, and radio-frequency power is 40-60W, adopts these process conditions to prepare I layer Nano thin film, and its crystalline state content is between 50 ± 5%, and the crystalline state peak is at 509-518cm
-1Between, room-temperature conductivity reaches 10
1Ω
-1Cm
-1-10
2Ω
-1Cm
-1On the basis of above-mentioned technology, feed high-purity hydrogen H again
2The concentration of having diluted with hydrogen is 0.5% high-purity phosphine PH
3, its silane SiH
4, hydrogen H
2, phosphine PH
3The flow-rate ratio of these three kinds of working gass is 5: 100: 5-15 (SCCM), and adopt these process conditions to prepare N layer Nano thin film, its conductivity reaches 10
1Ω
-1Cm
-1-10
2Ω
-1Cm
-1On the basis of above-mentioned technology, with phosphine PH
3Change borine B into
2H
5Promptly feed high-purity hydrogen H
2The concentration of having diluted with hydrogen is 5% high-purity borine B
2H
5, its silane SiH
4, hydrogen H
2, borine B
2H
5The flow-rate ratio of these three kinds of working gass is 5: 100: 0.3-0.8 (SCCM), and Dc bias is 100-300V, adopts these process conditions to prepare P layer Nano thin film, its conductivity reaches 10
1Ω
-1Cm
-1-10
2Ω
-1Cm
-1
5. the ellipse garden of a kind of thin-film solar cell of nano silicon according to claim 1 polarised light is monitored the preparation method in real time; It is characterized in that: the concrete practice of step 4 is: adopt extinction type ellipse garden polarization flash ranging film thickness gauge principle, in the vacuum insulation chamber of work chamber both sides, the polarizer, quarter-wave plate and analyzer, laser are installed respectively; Wavelength 635nm laser is through the polarizer and quarter-wave plate; Through work chamber's the left window, get into work chamber and spend oblique incidence in sample surfaces with 60 °-80 ° again, its folded light beam gets into right forevacuum chamber through work chamber's right side window; Be incident in photomultiplier or optical semiconductor battery and surveyed its light intensity and change through analyzer again for the film of setting; Its light intensity was zero when given ellipsometric parameter Δ, Ψ were arranged promptly corresponding to certain polarizer angle and analyzer angle, and in thin film growth process, its light intensity changes has corresponding variation; When light intensity is zero; The film of just growing and setting, shutdown at this moment stops film growth, thereby reaches the purpose of real-time monitoring film growth.
6. the ellipse garden of a kind of thin-film solar cell of nano silicon according to claim 1 polarised light is monitored the preparation method in real time, and it is characterized in that: the concrete practice of step 5 is: when adopting thermal evaporation method to prepare electrode, and system's base vacuum: 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～500 ℃, and thermal resistance evaporation or electron beam evaporation are even all right; When adopting magnetically controlled sputter method to prepare electrode, system's base vacuum: 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～500 ℃, sputtering current 0.4-0.8A, sputtering voltage 350-450V, working gas Ar
2, operating air pressure 0.5-3Pa; Screen printing technique adopts general screen printing technique; When adopting magnetically controlled sputter method to prepare ITO electrically conducting transparent membrane electrode, system's base vacuum: 8.0 * 10
-4Below the Pa, sample temperature is 200 ℃～500 ℃, feeds high-purity argon gas Ar and high purity oxygen gas O
2, the flow-rate ratio of these two kinds of working gas is 100: 1.5-2.5 (SCCM), operating air pressure 0.5-3Pa; Sputtering current 0.4-0.6A, sputtering voltage 350-420V; It is that ITO or Al-Doped ZnO are AZO that Coating Materials adopts electrically conducting transparent membrane material indium tin oxide, and upper electrode material adopts metal film such as aluminium film or each metal film composite membrane such as titanium palladium-silver.
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