CN101609796A - The manufacture method of film formation method and thin-film solar cells - Google Patents
The manufacture method of film formation method and thin-film solar cells Download PDFInfo
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- CN101609796A CN101609796A CNA2008101267211A CN200810126721A CN101609796A CN 101609796 A CN101609796 A CN 101609796A CN A2008101267211 A CNA2008101267211 A CN A2008101267211A CN 200810126721 A CN200810126721 A CN 200810126721A CN 101609796 A CN101609796 A CN 101609796A
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Abstract
The invention discloses the manufacture method of a kind of film formation method and thin-film solar cells, comprising: substrate is provided; At described substrate surface deposition seeding layer; At described seeding layer surface deposition amorphous silicon layer; In high pressure hydrogen atmosphere, carry out thermal anneal process, change described amorphous silicon layer into microcrystal silicon layer.Film formation method of the present invention can form microcrystalline silicon film in a kind of more simple and reliable mode.
Description
Technical field
The present invention relates to the photovoltaic solar cell technical field, the manufacture method of particularly a kind of film formation method and thin-film solar cells.
Background technology
Along with the worsening shortages of the energy, the development and use of renewable green energy resource more and more are subjected to people's attention, are subjected to common people's favor especially especially with the utilization of solar energy.Photovoltaic device (solar cell) as the solar energy converting media changes into electric energy by photoelectric effect with sunlight, incandescence or fluorescence etc.This conversion be when irradiate light when the photovoltaic device, luminous energy by the active region of device absorb produce electronics and the hole right, these electronics and hole are separated by the built-in electric field of device then, collect the output electric energy by peripheral circuit.
Recent years, thin-film solar cells and large tracts of land photovoltaic module cause common people's extensive concern all the more, amorphous silicon hydride (a-Si:H) and microcrystal silicon (μ c-Si:H) thin-film solar cells that occurs in recent years particularly is with its large tracts of land, low cost, can be created on the frivolous substrate and be easy to lay the extensive use of advantage in commerce and dwelling house facility such as installation and demonstrated great potential.Structure according to known amorphous silicon hydride and microcrystalline silicon film solar cell, internal electric field is to produce in the p-i-n structure that contains p type, intrinsic (i) type and the n type rete made by amorphous silicon and/or microcrystal silicon, when light of proper wavelength is absorbed, will generate electron-hole pair in the non-doping type intrinsic i layer.Under the effect of built-in electric field, electronics-hole is separated, and electron stream is to n type conduction region, and the hole flows to p type conduction region, and this electronics-hole stream just produces photovoltage.
Semi-conducting material as the non-doping type intrinsic i layer of thin-film solar cells requires to have stronger light absorpting ability, can produce a large amount of electron hole pairs, as much as possible incident optical energy is changed into useful electric energy, and then improve the photoelectric conversion efficiency of thin-film solar cells.In this respect, microcrystal silicon has higher carrier mobility, and can absorb more longwave optical, and photoelectric conversion efficiency will be higher than amorphous silicon, and can not occur the photic attenuating effect of amorphous silicon material film under illumination, and performance is more stable.The material that uses in microcrystal silicon and other solar-energy photo-voltaic cell, particularly compare with polysilicon, can absorb most solar radiation under several microns the thickness being no more than, and manufacturing process is simple, cost is low, so microcrystal silicon is an ideal material of making thin-film solar cells.
The existing method that forms microcrystal silicon mainly is the method that directly deposits, and comprises radio frequency or very high frequency(VHF) plasma-reinforced chemical vapor deposition (PECVD), hot-wire chemical vapor deposition (HW-CVD) and electron cyclotron resonace chemical vapor deposition (ECR-CVD).Pecvd process is to utilize hydrogen (H
2) dilution silane (SiH
4) gas is source gas, substrate temperature is between 150～260 ℃, utilize radio-frequency (RF) energy that reacting gas is excited and be plasma, directly deposit the formation microcrystalline silicon film at substrate surface, yet this method for uniformity and the stability that guarantees film will have lower deposition rate usually, for example is lower than when large-area film deposition
, this utmost point is unfavorable for enhancing productivity and reducing manufacturing cost.HW-CVD technology mainly is to utilize H
2The SiH of dilution
4Or SiF
4Gas is heated to be deposited on behind the pyrolysis by wire and forms microcrystal silicon on the substrate, yet there is the problem of metal ion pollution microcrystal silicon material in this method, and the wire life-span is limited, needs often to change, and is not easy to continuously large-scale industrial production reliably.ECR-CVD technology is with H
2The silane SiH of dilution
4Gas is source gas, utilizes the high density ion flow to deposit the Si atom near the substrate the ecr plasma district and forms microcrystalline silicon film.But the degree of crystallinity of this method is lower, and the production equipment complexity, is unfavorable for reducing production costs.
Summary of the invention
The object of the present invention is to provide a kind of film formation method, can form microcrystalline silicon film in a kind of more simple and reliable mode.
Membrane according to the invention formation method comprises:
Substrate is provided;
At described substrate surface deposition seeding layer;
At described seeding layer surface deposition amorphous silicon layer;
In high pressure hydrogen atmosphere, carry out thermal anneal process, change described amorphous silicon layer into microcrystal silicon layer.
Preferably, the pressure of hydrogen is 100～800 atmospheric pressure.
Preferably, the temperature of described thermal annealing is 250 ℃～300 ℃, and the time of annealing in process is 1～10 hour.
Optionally, described seeding layer utilizes the pecvd process deposition to form by the mist of hydrogen and silane, and the deposit thickness of described seeding layer is 20 nanometers～300 nanometers.
Preferably, the ratio of described hydrogen and silane is 30: 1 to 200: 1.
Preferably, the process conditions of described pecvd process comprise that plasma exciatiaon power is 200mw/cm
2～600mw/cm
2, the pressure in the reative cell is 0.3Torr～20Torr, temperature is 100 ℃～300 ℃.
Optionally, described amorphous silicon layer utilizes the pecvd process deposition to form by the mist of hydrogen and silane, and the frequency range in plasma excitation source is 4MHz～200MHz.
Film formation method of the present invention is applicable to the manufacture method of thin-film solar cells, particularly forms the method for the i layer in the p-i-n structure, also comprises the method that forms p layer and n layer.
According to the present invention, a kind of manufacture method of thin-film solar cells is provided, after the electrode, described method comprises before glass baseplate surface forms electrically conducting transparent:
Electrode surface deposition bottom is the p type doped amorphous silicon layer of seeding layer before described electrically conducting transparent;
In high pressure hydrogen atmosphere, carry out annealing in process and form microcrystal silicon p layer;
In described microcrystal silicon p laminar surface deposition bottom is the intrinsic amorphous silicon i layer of seeding layer;
In high pressure hydrogen atmosphere, carry out annealing in process and form microcrystal silicon i layer;
In described microcrystal silicon i laminar surface deposition bottom is the n type doped amorphous silicon layer of seeding layer;
In high pressure hydrogen atmosphere, carry out annealing in process and form microcrystal silicon n layer.
According to the present invention, the manufacture method of the another kind of thin-film solar cells that provides, after the electrode, described method comprises before glass baseplate surface forms electrically conducting transparent:
The n type doped amorphous silicon layer that intrinsic amorphous silicon i layer that is seeding layer for the p type doped amorphous silicon layer of seeding layer, bottom bottom electrode surface deposits successively before electrically conducting transparent and bottom are seeding layer;
In high pressure hydrogen atmosphere, described each layer carried out thermal anneal process, form microcrystal silicon p layer, microcrystal silicon i layer and microcrystal silicon n layer.
The present invention also comprises the semiconductor structure that is used to utilize above-mentioned film formation method formation microcrystal silicon, comprise substrate, and at the seeding layer of described substrate surface deposition, with amorphous silicon layer at described seeding layer surface deposition, the crystal grain of described seeding layer is small, and the thermal anneal process process that is used under hydrogen gas environment changes described amorphous silicon layer into microcrystal silicon layer.
Compared with prior art, the present invention has the following advantages:
The hydrogenation non crystal silicon film that the bottom is a seeding layer that film formation method of the present invention at first forms on substrate carries out annealing in process then, thereby obtains being suitable for being used as the microcrystalline hydrogenated silicon rete of opto-electronic conversion in hydrogen gas environment.The lattice structure of silicon at first begins to reconfigure at the interface of seeding layer in the annealing process of hydrogen gas environment, makes young crystalline substance constantly enlarge, and then makes whole amorphous silicon layer change microcrystal silicon layer into.Compare with direct deposition micro crystal silicon layer, utilize the seeding layer formation microcrystal silicon layer of under hydrogen gas environment, annealing, can make production process more simple and efficient, thereby improve production efficiency.The abundant environment of hydrogen makes that the defective of grain surface in time obtains repairing the higher electronic defects density that microcrystal silicon had of having avoided common direct growth to go out.In addition, film formation method of the present invention can allow to contain high relatively impurity in the silicon materials and the performance that do not influence microcrystal silicon, and less demanding to material and facility helps the depositing large-area film, and reduce manufacturing cost.
Description of drawings
By the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose, feature and advantage of the present invention will be more clear.Reference numeral identical in whole accompanying drawings is indicated identical part.Painstakingly do not draw accompanying drawing in proportion, focus on illustrating purport of the present invention.In the accompanying drawings, for clarity sake, amplified the thickness of layer.
Fig. 1 is the flow chart of film formation method of the present invention;
Fig. 2 to Fig. 4 is the cross-sectional view of explanation film formation method of the present invention;
Fig. 5 a to Fig. 5 h is the cross-sectional view of explanation thin-film solar cells manufacture method of the present invention.
Described diagrammatic sketch is illustrative, and nonrestrictive, can not excessively limit protection scope of the present invention at this.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar popularization under the situation of intension of the present invention.Therefore the present invention is not subjected to the restriction of following public specific embodiment.
Fig. 1 is the flow chart of film formation method of the present invention, as shown in Figure 1, film formation method of the present invention at first provides a substrate (step S101), and this substrate can be a transparent glass substrate, also can any surface will form the substrate (substrate) of microcrystalline silicon film, for example, if will form microcrystal silicon p layer, substrate is the preceding electrode tco layer of electrically conducting transparent so, if will form microcrystal silicon i layer, substrate is exactly the p layer so, is determined on a case-by-case basis; Next form seeding layer (step S102) at substrate surface, this seeding layer can utilize pecvd process or HW-CVD technology to form, and guarantee that this seeding layer has less crystal grain; Form amorphous silicon layer (step S103) on the seeding layer surface then, the deposition process of high-quality amorphous silicon membrane is a lot, comprise low-pressure chemical vapor phase deposition (LPCVD), plasma enhanced CVD (PECVD), hot-wire chemical vapor deposition (HW-CVD) or the like, these method technical maturities, deposition rate are fast, overcome the shortcoming of the low and lack of homogeneity of microcrystalline silicon deposition speed, improved production efficiency; In ensuing processing step, in being not less than 100 atmospheric hydrogen gas environments, the whole base plate that comprises seeding layer and amorphous silicon layer is carried out thermal anneal process (step S104) being lower than under 300 ℃ the temperature, thereby obtain the microcrystalline hydrogenated silicon film.
Fig. 2 to Fig. 4 is the cross-sectional view of explanation the inventive method.At first referring to shown in Figure 2, on substrate or substrate 100 surfaces, utilize plasma enhanced CVD (PECVD) process deposits seeding layer 101, the source gas that deposits this seeding layer 101 is the mist of hydrogen and silane, in the mist, the ratio of hydrogen and silane is 30: 1 to 200: 1, for example 100: 1, i.e. and H
2: SiH
4=100: 1, the plasma exciatiaon power in RF excited source is 200～600mw/cm
2, the pressure in the reative cell remains on 0.3～20Torr, and temperature is 100～300 ℃.The deposit thickness of seeding layer 101 is 20～300 nanometers.Then, utilize pecvd process to continue deposited amorphous silicon layer 102 on seeding layer 101 surfaces, the high frequency pumping source is adopted in the plasma excitation source, frequency range is 4～200MHz, for example 13.56MHz, 27MHz, to increase deposition rate, plasma exciatiaon power is 200～600mw/cm
2, the pressure in the reative cell remains on 0.3～5Torr, and temperature is 100～300 ℃.The deposit thickness of amorphous silicon layer 102 is 1～5 micron.The thickness of seeding layer 101 is compared extremely thin with the thickness of amorphous silicon layer 102, therefore seeding layer 101 is the amorphous silicon layer 110 of seeding layer thereon bottom the amorphous silicon layer 102 of deposition can be considered jointly, the effect of seeding layer 101 is that the lattice structure of amorphous silicon layer 102 is changed, guide its crystallization again, growth crystal grain forms microcrystal silicon layer.
Next as shown in Figure 3, the substrate 100 that the surface is had seeding layer 101 and amorphous silicon layer 102 is put into reaction under high pressure chamber 200, and places on the pedestal 400, and pedestal 400 has heating function, substrate 100 can be heated to required temperature.In reaction under high pressure chamber 200, feed 100～800 atmospheric high pressure hydrogens 300, in preferred embodiment, can add some inert gases in the high pressure hydrogen 300, for example argon gas and/or helium.And substrate 100 is heated to 250～300 ℃ temperature, and seeding layer 101 and amorphous silicon layer 102 are carried out annealing in process, the time of annealing in process is 1～10 hour.In the annealing process of hydrogen gas environment, the lattice structure of silicon at first begins to reconfigure at the interface 115 of seeding layer 101 with amorphous silicon layer 102, the crystal grain of seeding layer 101 is under the help of high pressure hydrogen, lattice structure constantly changes, crystal grain constantly enlarges the amorphous silicon layer 102 that also extends to gradually on it, and then make whole amorphous silicon layer 102 change microcrystalline hydrogenated silicon layer 150 into, as shown in Figure 4.
The formation method of the microcrystalline silicon film of the invention described above is applicable to the manufacture method of thin-film solar cells, is not only the i layer that forms in the p-i-n structure, also can be used to form p layer and n layer.Fig. 5 a to Fig. 5 h is the cross-sectional view of explanation thin-film solar cells manufacture method of the present invention.Referring to Fig. 5 a to Fig. 5 h, in the manufacture method of thin-film solar cells of the present invention, before glass baseplate surface forms electrically conducting transparent after the electrode, electrode 500 surfaces utilize pecvd process deposition bottom for seeding layer 501, the top hydrogenated amorphous silicon layer 510 for p type impurity doped amorphous silicon layer 502, shown in Fig. 5 a before electrically conducting transparent; In high pressure hydrogen atmosphere, carry out annealing in process then and form microcrystalline hydrogenated silicon p layer 511, shown in Fig. 2 b; Utilize pecvd process to continue the deposition bottom then for seeding layer 503, top hydrogenated amorphous silicon layer 520, shown in Fig. 5 c for intrinsic amorphous silicon layer 504 on the p of microcrystalline hydrogenated silicon layer 511 surface; In high pressure hydrogen atmosphere, carry out annealing in process and form microcrystalline hydrogenated silicon i layer 521, shown in Fig. 5 d; Continue to utilize pecvd process deposition bottom for seeding layer 505, top hydrogenated amorphous silicon layer 530, shown in Fig. 5 e again for n type doped amorphous silicon in microcrystalline hydrogenated silicon i layer 521 surface; And in high pressure hydrogen atmosphere, carry out the n layer 531 that annealing in process forms microcrystalline hydrogenated silicon, shown in Fig. 5 f.
In other embodiments, can be before electrically conducting transparent electrode 500 surfaces utilize pecvd process to deposit the hydrogenated amorphous silicon layer 530 that mixes for the n type of seeding layer for the intrinsic amorphous silicon layer 520 of seeding layer and bottom for the hydrogenated amorphous silicon layer 510 of the p type doping impurity of seeding layer, bottom in the bottom successively, shown in Fig. 5 g; In high pressure hydrogen atmosphere, above-mentioned each layer carried out thermal anneal process then, thereby after annealing process finishes, form p layer 511, i layer 521 and the n layer 531 of microcrystalline hydrogenated silicon simultaneously, shown in Fig. 5 h.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction.For example, although each in the accompanying drawings layer all be smooth and thickness almost equal, this only is that principle of the present invention is described for convenience and clearly.Any those of ordinary skill in the art are not breaking away under the technical solution of the present invention scope situation, all can utilize the technology contents of above-mentioned announcement that technical solution of the present invention is made many possible changes and modification, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical solution of the present invention, all still belongs in the protection range of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did according to technical spirit of the present invention.
Claims (10)
1, a kind of film formation method comprises:
Substrate is provided;
At described substrate surface deposition seeding layer;
At described seeding layer surface deposition amorphous silicon layer;
In high pressure hydrogen atmosphere, carry out thermal anneal process, change described amorphous silicon layer into microcrystal silicon layer.
2, the method for claim 1 is characterized in that: the pressure of hydrogen is 100～800 atmospheric pressure.
3, the method for claim 1 is characterized in that: the temperature of described thermal annealing is 250 ℃～300 ℃, and the time of annealing is 1～10 hour.
4, the method for claim 1 is characterized in that: described seeding layer utilizes the pecvd process deposition to form by the mist of hydrogen and silane, and the deposit thickness of described seeding layer is 20 nanometers～300 nanometers.
5, method as claimed in claim 4 is characterized in that: the ratio of described hydrogen and silane is 30: 1 to 200: 1.
6, method as claimed in claim 4 is characterized in that: the process conditions of described pecvd process comprise that plasma exciatiaon power is 200mw/cm
2～600mw/cm
2, the pressure in the reative cell is 0.3Torr～20Torr, temperature is 100 ℃～300 ℃.
7, the method for claim 1 is characterized in that: described amorphous silicon layer utilizes the pecvd process deposition to form by the mist of hydrogen and silane, and the frequency range in plasma excitation source is 4MHz～200MHz.
8, a kind of manufacture method that adopts the thin-film solar cells of the described film of claim 1 formation method, after the electrode, described method comprises before glass baseplate surface forms electrically conducting transparent:
Electrode surface deposition bottom is the p type doped amorphous silicon layer of seeding layer before described electrically conducting transparent;
In high pressure hydrogen atmosphere, carry out annealing in process and form microcrystal silicon p layer;
In described microcrystal silicon p laminar surface deposition bottom is the intrinsic amorphous silicon i layer of seeding layer;
In high pressure hydrogen atmosphere, carry out annealing in process and form microcrystal silicon i layer;
In described microcrystal silicon i laminar surface deposition bottom is the n type doped amorphous silicon layer of seeding layer;
In high pressure hydrogen atmosphere, carry out annealing in process and form microcrystal silicon n layer.
9, a kind of manufacture method that adopts the thin-film solar cells of the described film of claim 1 formation method, after the electrode, described method comprises before glass baseplate surface forms electrically conducting transparent:
The n type doped amorphous silicon layer that intrinsic amorphous silicon i layer that is seeding layer for the p type doped amorphous silicon layer of seeding layer, bottom bottom electrode surface deposits successively before electrically conducting transparent and bottom are seeding layer;
In high pressure hydrogen atmosphere, described each layer carried out thermal anneal process, form microcrystal silicon p layer, microcrystal silicon i layer and microcrystal silicon n layer.
10, a kind of semiconductor structure, comprise substrate, and at the seeding layer of described substrate surface deposition, with amorphous silicon layer at described seeding layer surface deposition, the crystal grain of described seeding layer is small, and the thermal anneal process process that is used under hydrogen gas environment changes described amorphous silicon layer into microcrystal silicon layer.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234786A (en) * | 2010-04-27 | 2011-11-09 | 东京毅力科创株式会社 | Amorphous silicon film formation method and amorphous silicon film formation apparatus |
| DE102010062383A1 (en) | 2010-12-03 | 2012-06-06 | Evonik Degussa Gmbh | Method for converting semiconductor layers |
| DE102010062386A1 (en) | 2010-12-03 | 2012-06-06 | Evonik Degussa Gmbh | Method for converting semiconductor layers |
| CN102651399A (en) * | 2011-07-19 | 2012-08-29 | 京东方科技集团股份有限公司 | Microcrystal amorphous silicon composite thin film transistor and manufacturing method thereof |
| CN103238219A (en) * | 2010-11-16 | 2013-08-07 | 东电电子太阳能股份公司 | Improved alpha-Si:H absorber layer for alpha-Si single- and multijunction thin film silicon solar cell |
| CN111564365A (en) * | 2020-04-10 | 2020-08-21 | 中国科学院微电子研究所 | Method for depositing film, application of method and method for forming semiconductor active region |
| CN113921378A (en) * | 2021-09-29 | 2022-01-11 | 惠科股份有限公司 | Preparation method of microcrystalline silicon, preparation method of thin film transistor and array substrate |
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| AUPM982294A0 (en) * | 1994-12-02 | 1995-01-05 | Pacific Solar Pty Limited | Method of manufacturing a multilayer solar cell |
| CN101237005A (en) * | 2007-01-29 | 2008-08-06 | 北京行者多媒体科技有限公司 | Forming method for micro crystal silicon film |
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| CN102234786A (en) * | 2010-04-27 | 2011-11-09 | 东京毅力科创株式会社 | Amorphous silicon film formation method and amorphous silicon film formation apparatus |
| CN102234786B (en) * | 2010-04-27 | 2014-09-10 | 东京毅力科创株式会社 | Amorphous silicon film formation method and amorphous silicon film formation apparatus |
| CN103238219A (en) * | 2010-11-16 | 2013-08-07 | 东电电子太阳能股份公司 | Improved alpha-Si:H absorber layer for alpha-Si single- and multijunction thin film silicon solar cell |
| DE102010062383A1 (en) | 2010-12-03 | 2012-06-06 | Evonik Degussa Gmbh | Method for converting semiconductor layers |
| DE102010062386A1 (en) | 2010-12-03 | 2012-06-06 | Evonik Degussa Gmbh | Method for converting semiconductor layers |
| WO2012072406A1 (en) | 2010-12-03 | 2012-06-07 | Evonik Degussa Gmbh | Method for converting semiconductor layers |
| WO2012072401A1 (en) | 2010-12-03 | 2012-06-07 | Evonik Degussa Gmbh | Method for converting semiconductor layers |
| CN102651399A (en) * | 2011-07-19 | 2012-08-29 | 京东方科技集团股份有限公司 | Microcrystal amorphous silicon composite thin film transistor and manufacturing method thereof |
| CN102651399B (en) * | 2011-07-19 | 2015-06-17 | 京东方科技集团股份有限公司 | Microcrystal amorphous silicon composite thin film transistor and manufacturing method thereof |
| CN111564365A (en) * | 2020-04-10 | 2020-08-21 | 中国科学院微电子研究所 | Method for depositing film, application of method and method for forming semiconductor active region |
| CN113921378A (en) * | 2021-09-29 | 2022-01-11 | 惠科股份有限公司 | Preparation method of microcrystalline silicon, preparation method of thin film transistor and array substrate |
| CN113921378B (en) * | 2021-09-29 | 2022-08-23 | 惠科股份有限公司 | Preparation method of microcrystalline silicon, preparation method of thin film transistor and array substrate |
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