CN110416344A - A kind of silicon substrate antimony trisulfide heterojunction solar battery and preparation method thereof - Google Patents
A kind of silicon substrate antimony trisulfide heterojunction solar battery and preparation method thereof Download PDFInfo
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- CN110416344A CN110416344A CN201910622847.6A CN201910622847A CN110416344A CN 110416344 A CN110416344 A CN 110416344A CN 201910622847 A CN201910622847 A CN 201910622847A CN 110416344 A CN110416344 A CN 110416344A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 86
- 239000010703 silicon Substances 0.000 title claims abstract description 86
- 229940007424 antimony trisulfide Drugs 0.000 title claims abstract description 67
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000758 substrate Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 22
- 230000005540 biological transmission Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims description 34
- 238000001704 evaporation Methods 0.000 claims description 34
- 238000000137 annealing Methods 0.000 claims description 20
- 238000002207 thermal evaporation Methods 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910015711 MoOx Inorganic materials 0.000 claims description 8
- 238000007740 vapor deposition Methods 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 230000005525 hole transport Effects 0.000 claims description 3
- 229910005855 NiOx Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 231100001261 hazardous Toxicity 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- 239000004332 silver Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
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- 235000013312 flour Nutrition 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 235000008216 herbs Nutrition 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000002574 poison Substances 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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- 229910052959 stibnite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero- junctions, X being an element of Group VI of the Periodic Table
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Abstract
The invention discloses a kind of silicon substrate antimony trisulfide heterojunction solar batteries, from top to bottom successively include preceding electrode, anti-reflection layer, electron transfer layer, silicon substrate, hole transmission layer and back electrode；The material of the electron transfer layer includes antimony trisulfide, and the silicon substrate is p-type monocrystalline silicon.Heterojunction solar battery of the present invention is using antimony trisulfide as electron transfer layer, and antimony trisulfide can be matched preferably with p-type silicon band structure, be conducive to the transmission of electronics, and the minority diffusion length of antimony trisulfide is big, can obtain biggish short circuit current.The invention also discloses a kind of preparation methods of silicon substrate antimony trisulfide heterojunction solar battery, this method simple process, low temperature, safe and environment-friendly, Yi Shixian, and cost advantage is significant, omits hazardous gas used in High temperature diffusion p-n junction technique and the preparation of HIT battery etc..
Description
Technical field
The present invention relates to a kind of heterojunction solar batteries and preparation method thereof, and in particular to a kind of silicon substrate antimony trisulfide hetero-junctions
Solar cell and preparation method thereof.
Background technique
Solar energy has cleaning, advantage that is safe, resourceful and not influenced by objective geographic factor, it is considered to be
21 century most important renewable energy and green novel energy source.Solar cell is as a kind of important electrooptical device, to solution
Certainly energy shortage and its cause environmental pollution, climatic deterioration the problems such as be of great significance.
Photovoltaic industry has obtained high speed development in recent years, and crystal silicon solar energy battery has manufacture craft maturation, property at present
The advantages such as energy stabilization, transfer efficiency height, occupy leading position, traditional Al-BSF battery, PERC in solar battery in the market
The homogeneities junction battery such as battery needs high temperature thermal diffusion to form p-n junction, there is certain thermal damage to silicon wafer；It is highly doped simultaneously to lead to height
Auger recombination, limit the promotion that battery opens pressure.HIT battery uses a variety of inflammable, explosive, hypertoxic gases, and electrode low temperature
The problems such as silver paste is expensive, at high cost there are battery.Exempt from adulterate antisymmetry heterojunction battery concept in 2015 for the first time
It is suggested, it is advantageous that the emitter of battery and back surface field do not have doping process, DASH battery is a current research hotspot,
Carrier selective exposure has carried out a large amount of research in silicon/crystalline silicon heterojunction battery.It is selectively transmitted based on carrier novel
The material of silicon based hetero-junction used in battery is more diversified, and preparation process can also accomplish more to simplify and energy conservation, and green
Environmental protection, while being also able to achieve higher transformation efficiency.
Antimony trisulfide is a kind of V-VI race direct band-gap semicondictor material that property is stable, rich content, safe nothing in the earth's crust
Poison.Band gap width is moderate, is easy to regulate and control, and covers most of visible light, therefore the material is considered as very potential answers
Used in one of solar cell material, solution is generally configured to using chemical bath deposition legal system with the compound of sulfur-bearing and antimony at present
Standby vulcanization Sb film, is mainly used in hull cell.The preparation method for vulcanizing Sb film is still deficienter, and chemical deposition
Method preparation vulcanization Sb film is mostly amorphous state, and film thickness cannot be controlled accurately；Vulcanization Sb film is mainly used in hull cell,
Organic hole transport material layer is used mostly, so that stability test is poor, and is passed with the inorganic hole of antimony trisulfide film matches
Defeated layer only has the p-type semiconductor of only a few, limits antimony trisulfide in the application of inorganic thin film battery.Sb film is not vulcanized almost also not
In the silicon substrate heterojunction solar cell applied.
Summary of the invention
A kind of silicon substrate antimony trisulfide hetero-junctions is provided it is an object of the invention to overcome the shortcomings of the prior art place
Solar cell and preparation method thereof.
To achieve the above object, the technical scheme adopted by the invention is as follows: a kind of silicon substrate antimony trisulfide heterojunction solar battery, from
It successively include preceding electrode, anti-reflection layer, electron transfer layer, silicon substrate, hole transmission layer and back electrode under；The electron-transport
The material of layer includes antimony trisulfide, and the silicon substrate is p-type monocrystalline silicon.
The electron transfer layer of silicon substrate antimony trisulfide heterojunction solar battery of the present invention uses antimony trisulfide, inventor's discovery
Antimony trisulfide can be matched preferably with p-type silicon band structure, be conducive to the transmission of electronics, and the minority diffusion length of antimony trisulfide is big, can
To obtain biggish short circuit current.The silicon substrate is the p-type monocrystalline silicon of<100>crystal orientation.Preferably, the electron transfer layer
With a thickness of 1~100nm.Film thickness influences whether the efficiency of battery, and with the increase of thickness, dropping after increasing first occurs in battery efficiency
Low phenomenon.
Preferably, the electron transfer layer with a thickness of 4~15nm.It is highly preferred that the electron transfer layer with a thickness of
4.5~6.5nm.Most preferably, the electron transfer layer with a thickness of 5.5nm.
Preferably, the electron transfer layer is vulcanization Sb film, and the vulcanization Sb film is prepared using thermal evaporation；
The technological parameter of the thermal evaporation are as follows: the temperature of silicon substrate is 20~400 DEG C, and vacuum degree is 1 × e-2~1 × e-5Pa, evaporation rate
ForPreferably, the evaporation rate isIt is highly preferred that the evaporation rate is
In the thickness control and purity of vulcanization Sb film advantageously, and vacuum environment advantageously reduces silicon to this method
The pollution on piece surface；Material used in the novel silicon base hetero-junction solar cell selectively transmitted based on carrier is more diversified, solution
The certainly limited disadvantage of inorganic transport layers in hull cell, application range of the developing antimony trisulfide material in field of batteries.
Preferably, the material of the preceding electrode is at least one of Ag, Au and Pd.
Preferably, the anti-reflection layer is transparent conductive metal oxide tco layer, and the TCO is made of ITO, AZO or FTO.
Anti-reflection layer primarily serves the effect for collecting transverse current, and itself and silver and Sb2S3Contact resistance it is smaller, can get lower
Series resistance.
Preferably, the hole transmission layer is high work function transition metal oxide composition；The high work function transition gold
Category oxide is MoOx、V2Ox、WOxOr NiOx.High work function transition metal oxide and silicon base layers form Ohmic contact.
Preferably, the material of the back electrode is at least one of Ag, Au and Pd.
Preferably, the preceding electrode with a thickness of 10nm~2 μm；The anti-reflection layer with a thickness of 10nm~2 μm；The sky
Cave transport layer with a thickness of 2~500nm；The back electrode with a thickness of 10nm~2 μm.
Another object of the present invention is to provide a kind of preparation method of silicon substrate antimony trisulfide heterojunction solar battery, packets
Include following steps:
(1), in the surface of silicon substrate vapor deposition vulcanization Sb film, N-shaped antimony trisulfide electron transfer layer is formed；
(2), anti-reflection layer is prepared in antimony trisulfide film surface magnetron sputtering method；
(3), electrode is prepared by silk-screen printing or thermal evaporation in anti-reflection layer surface, as preceding electrode；
(4), transition metal oxide is deposited at the silicon substrate back side, ohmic contact layer is formed, as hole transmission layer；
(5), continue silk-screen printing on the hole transport layer or thermal evaporation prepares metal layer, as back electrode.
Preferably, in step (2), the technological parameter of the magnetron sputtering method are as follows: the temperature of silicon substrate is 20~400 DEG C,
Background vacuum is 1 × e-2~1 × e-5Pa, sputtering power are 10~200W, and argon flow is 10~30sccm, with a thickness of
10nm~2um；
Preferably, in step (3), (4) and (5), the technological parameter of the vapor deposition are as follows: the temperature of silicon substrate is 20~400
DEG C, vacuum degree is 1 × e-2~1 × e-5Pa, evaporation rate are
Preferably, step (2) further include to vulcanization Sb film and anti-reflection layer make annealing treatment, annealing temperature be 200~
400 DEG C, the time is 10~60min.The temperature of annealing has large effect to final battery performance obtained, inventors have found that
When annealing temperature is excessively high and too low, battery efficiency can be all reduced, when annealing temperature is 200-400 DEG C, battery efficiency is higher,
Especially when annealing temperature is 300 DEG C, battery efficiency highest.
The entire preparation process of the present invention avoids high-temperature process, and raw material rich reserves in preparation process, without toxic material
The use of material, the discharge of pollution-free substance, to environmental protection with it is energy saving highly beneficial, preparation process simply easily realizes.
The beneficial effects of the present invention are: it is described different the present invention provides a kind of silicon substrate antimony trisulfide heterojunction solar battery
Using antimony trisulfide as electron transfer layer, antimony trisulfide can be matched preferably with p-type silicon band structure, is conducive to matter connection solar cell
The minority diffusion length of the transmission of electronics, antimony trisulfide is big, can obtain biggish short circuit current.The present invention also provides a kind of silicon
The preparation method of base antimony trisulfide heterojunction solar battery, this method simple process, low temperature, safe and environment-friendly, Yi Shixian, and cost
Advantage is significant, omits hazardous gas used in High temperature diffusion p-n junction technique and the preparation of HIT battery etc..
Detailed description of the invention
Fig. 1 is the structural schematic diagram that Fig. 1 is solar cell described in Examples 1 to 6；Wherein, 1 is silicon substrate, and 2 pass for electronics
Defeated layer, 3 be anti-reflection layer, and 4 be hole transmission layer, and 5 be back electrode, and 6 be preceding electrode.
Fig. 2 is JV curve (AM 1.5,25 DEG C) of the solar cell under standard test condition in embodiment 2.
Fig. 3 is JV curve (AM 1.5,25 DEG C) of the solar cell under standard test condition in embodiment 3.
Fig. 4 is JV curve (AM 1.5,25 DEG C) of the solar cell under standard test condition in embodiment 4.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of embodiment of silicon substrate antimony trisulfide heterojunction solar battery of the present invention, silicon substrate antimony trisulfide described in the present embodiment
The structural schematic diagram of heterojunction solar battery as shown in Figure 1, successively include from top to bottom preceding electrode, anti-reflection layer, electron transfer layer,
Silicon substrate, hole transmission layer and back electrode；
The electron transfer layer is antimony trisulfide film layer, with a thickness of 5.5nm；The silicon substrate is p-type monocrystalline silicon；
The material of the preceding electrode and back electrode is silver, and thickness is 500nm；
The anti-reflection layer is ITO nesa coating, and the material of the hole transmission layer is MoOx, with a thickness of 10nm.
The preparation method of silicon substrate antimony trisulfide heterojunction solar battery described in the present embodiment the following steps are included:
(1) it substrate pretreatment: using p-type monocrystalline silicon as substrate, using aqueous slkali one texture-etching side, then carries out conventional clear
It washes, and is dried silicon wafer；
(2) preparation of electron transfer layer: being evaporation with antimony trisulfide with thermal evaporation in silicon substrate making herbs into wool wheat flour for antimony trisulfide layer
Source, underlayer temperature are room temperature, and vacuum degree is 8 × 10-4Pa evaporation rate is5.5nm is deposited.
(3) ITO nesa coating, silicon wafer the preparation of anti-reflection layer: are prepared in antimony trisulfide film surface using magnetron sputtering method
Substrate temperature is room temperature, and vacuum degree is 8 × 10-4Pa, sputtering power 100W, argon flow 10sccm；
(4) it anneals in nitrogen to antimony trisulfide layer and ITO layer, annealing temperature is 300 DEG C, annealing time 30min；
(5) preparation of electrode before: placing electrode mask plate on the transparent conductive layer surface of above-mentioned (3) preparation, utilizes
Thermal evaporation vapor deposition silver, electrode before preparation is silver-colored, the underlayer temperature of silicon wafer are room temperature, and vacuum degree is 2 × 10-3Pa, evaporation rate are500nm is deposited.
(6) transition metal oxide MoO the preparation of hole transmission layer: is deposited using thermal evaporation in the silicon wafer other sidex, with
MoO3As evaporation source, the underlayer temperature of silicon wafer is room temperature, and vacuum degree is 8 × 10-4Pa, evaporation rate areIt is formed
The MoO of 10nmxLayer, obtains good ohmic contact layer,
(7) preparation of back electrode: transition metal oxide MoOxThe other side is using thermal evaporation evaporation metal silver, with metallic silver
Underlayer temperature for evaporation source, silicon wafer is room temperature, and evaporation rate isForm the Ag layer of 500nm.
Embodiment 2
In order to probe into influence of the antimony trisulfide film thickness to battery efficiency, using condition same as Example 1, change step
Suddenly the annealing temperature of (4) tests the battery performance of different-thickness (4nm, 4.5nm, 5.5nm, 6.5nm, 15nm), sees Fig. 2.
Fig. 2 is JV curve (AM 1.5,25 of the solar cell of this difference antimony trisulfide film thickness under standard test condition
DEG C), figure it is seen that Film Thickness has arrived the open-circuit voltage (V of batteryoc), short circuit current (Jsc), with a thickness of
When 4.5~6.5nm, battery efficiency is preferable, and in the thickness of 5.5nm, battery efficiency is optimal.
Embodiment 3
In order to probe into influence of the annealing temperature to battery efficiency, using the identical condition of the present embodiment, (4) are changed the step
Annealing temperature tests the cell performance of different annealing temperature (200 DEG C, 300 DEG C, 400 DEG C, unannealed processing (As-deposited))
Can, see Fig. 3.
Fig. 3 is JV curve (AM 1.5,25 DEG C) of the solar cell under standard test condition under different annealing temperature, from figure
3 can be seen that annealing temperature to the open-circuit voltage (V of batteryoc), short circuit current (Jsc) and fill factor (FF) have an impact, especially
It is at 300 DEG C, battery efficiency is optimal.
Embodiment 4
In order to probe into influence of the evaporation rate to battery performance, using the identical condition of the present embodiment, (2) are changed the step
Evaporation rate is tested under different evaporation ratesBattery performance, test result is shown in
Fig. 4.
Fig. 4 be under the conditions of different evaporation rates solar cell obtained under standard test condition JV curve (AM 1.5,
25 DEG C) and dark-state under the conditions of JV curve, from fig. 4, it can be seen that open-circuit voltage (V of the deposition rate to batteryoc), short circuit current
(Jsc) and fill factor (FF) have an impact, InWhen, battery efficiency is optimal.
Embodiment 5
A kind of embodiment of silicon substrate antimony trisulfide heterojunction solar battery of the present invention, silicon substrate antimony trisulfide described in the present embodiment
The structural schematic diagram of heterojunction solar battery as shown in Figure 1, successively include from top to bottom preceding electrode, anti-reflection layer, electron transfer layer,
Silicon substrate, hole transmission layer and back electrode；
The electron transfer layer is antimony trisulfide film layer, with a thickness of 1nm；The silicon substrate is p-type monocrystalline silicon；
The material of the preceding electrode and back electrode is silver, and thickness is 10nm；
The anti-reflection layer is ITO nesa coating, and the material of the hole transmission layer is MoOx, with a thickness of 100nm.
The preparation method of silicon substrate antimony trisulfide heterojunction solar battery described in the present embodiment the following steps are included:
(1) it substrate pretreatment: using p-type monocrystalline silicon as substrate, using aqueous slkali one texture-etching side, then carries out conventional clear
It washes, and is dried silicon wafer；
(2) preparation of electron transfer layer: being evaporation with antimony trisulfide with thermal evaporation in silicon substrate making herbs into wool wheat flour for antimony trisulfide layer
Source, underlayer temperature are room temperature, and vacuum degree is 1 × 10-5Pa evaporation rate is1nm is deposited；
(3) ITO nesa coating, silicon wafer the preparation of anti-reflection layer: are prepared in antimony trisulfide film surface using magnetron sputtering method
Substrate temperature is room temperature, and vacuum degree is 1 × 10-5Pa, sputtering power 10W, argon flow 30sccm；
(4) it anneals in nitrogen to antimony trisulfide layer and ITO layer, annealing temperature is 300 DEG C, annealing time 10min；
(5) preparation of electrode before: placing electrode mask plate on the transparent conductive layer surface of above-mentioned (3) preparation, utilizes
Thermal evaporation vapor deposition silver, electrode before preparation is silver-colored, the underlayer temperature of silicon wafer are room temperature, and vacuum degree is 1 × 10-5Pa, evaporation rate are10nm is deposited.
(6) transition metal oxide MoO the preparation of hole transmission layer: is deposited using thermal evaporation in the silicon wafer other sidex, with
MoO3As evaporation source, the underlayer temperature of silicon wafer is room temperature, and vacuum degree is 1 × 10-5Pa, evaporation rate areIt is formed
The MoO of 100nmxLayer, obtains good ohmic contact layer,
(7) preparation of back electrode: transition metal oxide MoOxThe other side is using thermal evaporation evaporation metal silver, with metallic silver
Underlayer temperature for evaporation source, silicon wafer is room temperature, and evaporation rate isForm the Ag layer of 10nm.
Embodiment 6
A kind of embodiment of silicon substrate antimony trisulfide heterojunction solar battery of the present invention, silicon substrate antimony trisulfide described in the present embodiment
The structural schematic diagram of heterojunction solar battery as shown in Figure 1, successively include from top to bottom preceding electrode, anti-reflection layer, electron transfer layer,
Silicon substrate, hole transmission layer and back electrode；
The electron transfer layer is antimony trisulfide film layer, with a thickness of 100nm；The silicon substrate is p-type monocrystalline silicon；
The material of the preceding electrode and back electrode is silver, and thickness is 2 μm；
The anti-reflection layer is ITO nesa coating, and the material of the hole transmission layer is MoOx, with a thickness of 2 μm.
The preparation method of silicon substrate antimony trisulfide heterojunction solar battery described in the present embodiment the following steps are included:
(1) it substrate pretreatment: using p-type monocrystalline silicon as substrate, using aqueous slkali one texture-etching side, then carries out conventional clear
It washes, and is dried silicon wafer；
(2) preparation of electron transfer layer: being evaporation with antimony trisulfide with thermal evaporation in silicon substrate making herbs into wool wheat flour for antimony trisulfide layer
Source, underlayer temperature are room temperature, and vacuum degree is 1 × 10-2Pa, evaporation rate are100nm is deposited；
(3) ITO nesa coating, silicon wafer the preparation of anti-reflection layer: are prepared in antimony trisulfide film surface using magnetron sputtering method
Substrate temperature is room temperature, and vacuum degree is 1 × 10-2Pa, sputtering power 200W, argon flow 10sccm；
(4) it anneals in nitrogen to antimony trisulfide layer and ITO layer, annealing temperature is 300 DEG C, annealing time 60min；
(5) preparation of electrode before: placing electrode mask plate on the transparent conductive layer surface of above-mentioned (3) preparation, utilizes
Thermal evaporation vapor deposition silver, electrode before preparation is silver-colored, the underlayer temperature of silicon wafer are room temperature, and vacuum degree is 1 × 10-2Pa, evaporation rate are2 μm of vapor deposition.
(6) transition metal oxide MoO the preparation of hole transmission layer: is deposited using thermal evaporation in the silicon wafer other sidex, with
MoO3As evaporation source, the underlayer temperature of silicon wafer is room temperature, and vacuum degree is 1 × 10-2Pa, evaporation rate areForm 2 μ
The MoO of mxLayer, obtains good ohmic contact layer,
(7) preparation of back electrode: transition metal oxide MoOxThe other side is using thermal evaporation evaporation metal silver, with metallic silver
Underlayer temperature for evaporation source, silicon wafer is room temperature, and evaporation rate isForm 2 μm of Ag layer.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of silicon substrate antimony trisulfide heterojunction solar battery, which is characterized in that from top to bottom successively include preceding electrode, anti-reflection layer,
Electron transfer layer, silicon substrate, hole transmission layer and back electrode；The material of the electron transfer layer includes antimony trisulfide, the silicon substrate
Body is p-type monocrystalline silicon.
2. silicon substrate antimony trisulfide heterojunction solar battery as described in claim 1, which is characterized in that the thickness of the electron transfer layer
For 1~100nm；Preferably, the electron transfer layer with a thickness of 4~15nm；It is highly preferred that the thickness of the electron transfer layer
For 4.5~6.5nm.
3. silicon substrate antimony trisulfide heterojunction solar battery as described in claim 1, which is characterized in that the electron transfer layer is vulcanization
Sb film, the vulcanization Sb film are prepared using thermal evaporation；The technological parameter of the thermal evaporation are as follows: the temperature of silicon substrate
Degree is 20~400 DEG C, and vacuum degree is 1 × e-2~1 × e-5Pa, evaporation rate are
4. silicon substrate antimony trisulfide heterojunction solar battery as described in claim 1, which is characterized in that the material of the preceding electrode is
At least one of Ag, Au and Pd.
5. silicon substrate antimony trisulfide heterojunction solar battery as described in claim 1, which is characterized in that the anti-reflection layer is electrically conducting transparent
Metal oxide tco layer, the TCO are made of ITO, AZO or FTO.
6. silicon substrate antimony trisulfide heterojunction solar battery as described in claim 1, which is characterized in that the hole transmission layer is Gao Gong
Function transition metal oxide is constituted；The high work function transition metal oxide is MoOx、V2Ox、WOxOr NiOx。
7. silicon substrate antimony trisulfide heterojunction solar battery as described in claim 1, which is characterized in that the material of the back electrode is
At least one of Ag, Au and Pd.
8. silicon substrate antimony trisulfide heterojunction solar battery as described in claim 1, which is characterized in that the preceding electrode with a thickness of
10nm~2 μm；The anti-reflection layer with a thickness of 10nm~2 μm；The hole transmission layer with a thickness of 2~500nm；The back electricity
Pole with a thickness of 10nm~2 μm.
9. a kind of preparation method of the silicon substrate antimony trisulfide heterojunction solar battery as described in any one of claim 1~8, feature
It is, comprising the following steps:
(1), in the surface of silicon substrate vapor deposition vulcanization Sb film, N-shaped antimony trisulfide electron transfer layer is formed；
(2), anti-reflection layer is prepared in antimony trisulfide film surface magnetron sputtering method；
(3), electrode is prepared by silk-screen printing or thermal evaporation in anti-reflection layer surface, as preceding electrode；
(4), transition metal oxide is deposited at the silicon substrate back side, ohmic contact layer is formed, as hole transmission layer；
(5), continue silk-screen printing on the hole transport layer or thermal evaporation prepares metal layer, as back electrode.
10. the preparation method of silicon substrate antimony trisulfide heterojunction solar battery as claimed in claim 9, which is characterized in that following (a)~
Any one of (c):
(a) in step (2), the technological parameter of the magnetron sputtering method are as follows: the temperature of silicon substrate is 20~400 DEG C, base vacuum
Degree is 1 × e-2~1 × e-5Pa, sputtering power are 10~200W, and argon flow is 10~30sccm, with a thickness of 10nm~2um；
(b) in step (3), (4) and (5), the technological parameter of the vapor deposition are as follows: the temperature of silicon substrate is 20~400 DEG C, vacuum degree
For 1 × e-2~1 × e-5Pa, evaporation rate are
(c) step (2) further includes the steps that making annealing treatment vulcanization Sb film and anti-reflection layer, and the annealing temperature is 200
~400 DEG C, the time is 10~60min.
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| WO2003083955A1 (en) * | 2002-03-29 | 2003-10-09 | Ebara Corporation | Photovoltaic element and method of manufacturing the same |
| CN105932089A (en) * | 2016-06-24 | 2016-09-07 | 深圳大学 | Back contact silicon heterojunction solar cell without interface doping and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003083955A1 (en) * | 2002-03-29 | 2003-10-09 | Ebara Corporation | Photovoltaic element and method of manufacturing the same |
| CN105932089A (en) * | 2016-06-24 | 2016-09-07 | 深圳大学 | Back contact silicon heterojunction solar cell without interface doping and preparation method thereof |
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