CN102437224A - Amorphous silicon film battery of Schottky structure with dielectric layer and production method - Google Patents
Amorphous silicon film battery of Schottky structure with dielectric layer and production method Download PDFInfo
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- CN102437224A CN102437224A CN2011103929162A CN201110392916A CN102437224A CN 102437224 A CN102437224 A CN 102437224A CN 2011103929162 A CN2011103929162 A CN 2011103929162A CN 201110392916 A CN201110392916 A CN 201110392916A CN 102437224 A CN102437224 A CN 102437224A
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Abstract
The invention discloses an amorphous silicon film battery of a Schottky structure with a dielectric layer and a production method. The film battery comprises a transparent underlay, a front transparent conductive layer TCO, an ohmic contact layer p-a-Si:H, an active layer amorphous silicon i-a-Si: H or a micro crystalline silicon i-Mu c-Si: H, a dielectric layer and a back electrode Al. The invention also provides a production method of the film battery, which sequentially comprises the following steps such as cleaning of the underlay layer, sputtering and vacuum plating of the TCO layer, plasma enhanced chemical vapor deposition (PECVD) vacuum plating of the p-a-Si: H layer and the i-a-Si: H layer (or an i-Mu c-Si: H), and cleaning and vacuum vapor deposition (or spin coating) of the dielectric layer and the back electrode Al layer, and a finished product can be obtained through post treatment. By adopting the Schottky structure of an amorphous silicon film, and adding the dielectric layer, the absorption of the long-wavelength region of the solar spectrum can be improved, the absorption loss and the serial-connection resistance are reduced, and the open-circuit voltage and the filling factor can be improved; and the process is simple, and the manufacturing cost can be greatly reduced.
Description
Technical field
The present invention relates to a kind of hull cell, particularly a kind of amorphous silicon membrane battery and manufacture method that has the Schottky junction structure of dielectric layer.
Background technology
Amorphous silicon thin-film solar cell extensively receives people's attention owing to have advantages such as low cost, technology maturation.But minority carrierdiffusion length is short and photoelectric conversion efficiency is low, therefore needs to improve effective light absorption of amorphous silicon membrane battery and photoelectric conversion efficiency.
Most p-i-n structures that adopt use tco layer as transparency electrode exactly in the amorphous silicon membrane battery, and the p layer is as Window layer, and the i layer promptly is main light absorbing zone as the intrinsic layer of solar cell, forms the internal electric field that pn ties with the n layer, produces open circuit voltage.But doped layer p layer and n layer be to not directly effect of power transfer in the p-i-n structure, and the n layer has to absorb and causes power loss.
Because the amorphous silicon membrane optical band gap is 1.7eV, material itself is insensitive to the long-wavelength region, has therefore limited the photoelectric conversion efficiency of amorphous silicon battery.The effective way that addresses this problem is made lamination p-i-n battery exactly, on a p-i-n battery, deposits one or more p-i-n batteries exactly again.But increased the cost of manufacture of amorphous silicon battery like this, complex process.
Schottky junction structure in the amorphous silicon battery is owing to make simply, and cost is low, and along with the appearance of photovoltaic material, in the development of amorphous silicon battery, is playing the part of considerable role.
Traditional Schottky junction structure is sheet metal electrode, amorphous silicon active layer, passive electrode, utilizes the Schottky barrier of metal electrode and amorphous silicon to form internal electric field generation open circuit voltage.The production process of internal electric field no longer needs the n doped layer in the p-i-n structure, can avoid the absorption loss of n doped layer so fully.Wherein the sheet metal electrode side is a sensitive surface, therefore is called preceding Schottky junction structure again.
In traditional Schottky junction structure, exist because the pinning effect of the Fermi level that metal and unordered crack attitude cause, therefore can cause the deterioration of open circuit voltage and fill factor, curve factor.And the thin layer of preceding electrode has tangible light absorption.
In this case, obviously be difficult to control absorption loss and can't reach the effect that makes full use of solar spectrum.Therefore, in Schottky junction structure, how to reduce optical absorption loss, how to add one and have appropriate bandgap width and work function matching materials, reduce series resistance and strengthen carrier collection, can avoid pinning effect again, just become a problem demanding prompt solution.
Summary of the invention
The objective of the invention is in order to solve the problem that the spectrum utilance is not high, series resistance is big that above-mentioned existing amorphous silicon thin-film solar cell exists, and a kind of amorphous silicon membrane battery and manufacture method that has the Schottky junction structure of dielectric layer is provided.
The amorphous silicon membrane battery of the present invention's the Schottky junction structure that has dielectric layer is the back of the body Schottky junction structure that has dielectric layer that is made up of from the bottom up transparent substrates (glass), preceding transparency conducting layer TCO, ohmic contact layer p-a-Si:H, absorbed layer (active layer) i-a-Si:H or microcrystal silicon i-μ c-Si:H, dielectric layer LiF or polymer, back electrode Al.
Described transparent substrates adopts the glass of high transmission rate.
Transparency conducting layer TCO before described, light pass by battery from it and absorb, and serve as the electrode of battery again, require transmitance height, good conductivity, adopt the method preparation of sputter.Its THICKNESS CONTROL is at 100nm.In order to increase the sunlight impingement rate, reduce catoptrical effect, TCO is processed suede structure.
Described ohmic contact layer p-a-Si:H adopts p type amorphous silicon membrane, and with the preparation of PECVD method, its THICKNESS CONTROL is at 20nm.
What described absorbed layer (active layer) adopted is amorphous silicon or microcrystal silicon, and its THICKNESS CONTROL is at 200～400nm.
What described dielectric layer adopted is lithium fluoride or polymer, with the method preparation of vapor deposition or spin coating.Its THICKNESS CONTROL is at 0.2～4nm.Dielectric layer plays the enhancing light absorption, reduces the effect of series resistance, pinning effect and the boundary defect that can avoid metal to contact with amorphous silicon.
Described back electrode adopts the Al film, and with the method preparation of vapor deposition, film thickness monitoring is at 50～100nm.
The manufacture method of the amorphous silicon membrane battery of the present invention's the Schottky junction structure that has dielectric layer comprises the steps:
1, transparent substrates is cleaned: scrub, use 0.3% surfactant; Washing, processing procedure is, preceding feedwater 10s, draining 30s, the 90s that feeds water, totally twice, the US ultrasonic cleaning, frequency of ultrasonic is 35KHz, Rotary drying.
2, preceding transparency conducting layer sputter: the condition of preceding transparency conducting layer sputter is: target In
2O
3: SnO
2=90: 10, Ar throughput 400Sccm and O
2Throughput 0.6Sccm; Sputtering power is 0.30～0.75kW, and pressure is 0.65～0.85Pa, and temperature is 205～225 ℃; The oxygen of trace can change the crystalline state of film in the sputter procedure, reduces resistivity.
3, Cement Composite Treated by Plasma: the condition of Cement Composite Treated by Plasma is: pressure 165～175Pa, and power 500W, 225～235 ℃ of temperature, hydrogen or nitrogen fluoride 100%, Cement Composite Treated by Plasma 4min forms suede structure.
4, PECVD successive sedimentation p-a-Si:H film-amorphous silicon film or microcrystalline sillicon film: PECVD is a plasma reinforced chemical vapour deposition;
The condition of PECVD deposition p-a-Si:H film is: the doping ratio that mixes borine is 30%, and the boron atom with coordination mode Cheng Jian, makes the boron atom become effective acceptor impurity in the a-Si:H network.Underlayer temperature is 225～255 ℃, and radio-frequency power 200～250W, gas are silane 60%, hydrogen 40%, borine 30%, and growth air pressure is 85～95Pa;
The condition of PECVD deposited amorphous silicon fiml or microcrystalline sillicon film is: 250～300 ℃ of underlayer temperatures, radio-frequency power 200～250W, gas silane 70% and hydrogen 50%, growth air pressure 65～75Pa.
5, micro etch is cleaned: the micro etch cleaning condition is: million cleanings, washing, IPA steam drying, the etching that adopt 1.6MHz.Etching agent is HF: NH
4F: H
2O=0.17: 17.10: 82.73, its effect was to remove the silica on the a-Si top layer of easy oxidation, in order to avoid loose contact; Want the control time shorter after substrate cleans, because surperficial that expose to the open air is a-Si:H, in air, parks and can reoxidize, the time was less than 20 minutes; Also do not carry out film forming like overtime, then need heavily wash.
6, vacuum evaporation dielectric layer lithium fluoride or spin coating method thin polymer film: the condition of vacuum evaporation dielectric layer lithium fluoride or spin coating method thin polymer film is: lithium fluoride adopts molybdenum boat, and temperature is 200 ℃, uses crystal oscillator monitoring evaporation rate to be per minute 1 lattice;
The condition of polymer is: adopt 3, the polymer and the poly styrene sulfonate of 4-enedioxy thiophene monomer increase current density; Spin speed is 3000rpm/60s, 130 ℃ of annealing 10 minutes under atmospheric condition after the spin coating, annealing back cooling 3 minutes.
7, continuous evaporating-plating back electrode Al: in the vacuum evaporation back electrode Al step, aluminium purity is 99.999%, and the vapor deposition electric current is 2A, uses crystal oscillator monitoring evaporation rate to be per minute 10 lattice, vapor deposition pressure 8 * 10
-3Pa.
8, after the processing, obtain finished product.
Beneficial effect of the present invention: the present invention has adopted the Schottky junction structure of amorphous silicon membrane, has increased dielectric layer, has improved the absorption of sunlight spectrum in the long-wavelength region, has reduced absorption loss and series resistance, has improved open circuit voltage and fill factor, curve factor; Technology is simple, can reduce manufacturing cost significantly.
Description of drawings
Fig. 1 is the structural representation of the amorphous silicon membrane battery of the Schottky junction structure that has dielectric layer of the embodiment of the invention 1 preparation.
Fig. 2 is the structural representation of the amorphous silicon membrane battery of the Schottky junction structure that has dielectric layer of the embodiment of the invention 2 preparations.
Fig. 3 is the structural representation of the amorphous silicon membrane battery of the Schottky junction structure that has a dielectric layer of the present invention.
Embodiment
As shown in Figure 3, the amorphous silicon membrane battery of the present invention's the Schottky junction structure that has dielectric layer is the back of the body Schottky junction structure that has dielectric layer that is made up of from the bottom up transparent substrates (glass), preceding transparency conducting layer TCO, ohmic contact layer p-a-Si:H, absorbed layer (active layer) i-a-Si:H or microcrystal silicon i-μ c-Si:H, dielectric layer LiF or polymer, back electrode Al.
Described transparent substrates adopts the glass of high transmission rate.
Transparency conducting layer TCO before described, light pass by battery from it and absorb, and serve as the electrode of battery again, require transmitance height, good conductivity, adopt the method preparation of sputter.Its THICKNESS CONTROL is at 100nm.In order to increase the sunlight impingement rate, reduce catoptrical effect, TCO is processed suede structure.
Described ohmic contact layer p-a-Si:H adopts p type amorphous silicon membrane, and with the preparation of PECVD method, its THICKNESS CONTROL is at 20nm.
What described absorbed layer (active layer) adopted is amorphous silicon or microcrystal silicon, and its THICKNESS CONTROL is at 200～400nm.
What described dielectric layer adopted is lithium fluoride or polymer, with the method preparation of vapor deposition or spin coating.Its THICKNESS CONTROL is at 0.2～4nm.Dielectric layer plays the enhancing light absorption, reduces the effect of series resistance, pinning effect and the boundary defect that can avoid metal to contact with amorphous silicon.
Described back electrode adopts the Al film, and with the method preparation of vapor deposition, film thickness monitoring is at 50～100nm.
The manufacture method of the amorphous silicon membrane battery of the present invention's the Schottky junction structure that has dielectric layer comprises the steps:
1, transparent substrates is cleaned: scrub, use 0.3% surfactant; Washing, processing procedure is, preceding feedwater 10s, draining 30s, the 90s that feeds water, totally twice, the US ultrasonic cleaning, frequency of ultrasonic is 35KHz, Rotary drying.
2, preceding transparency conducting layer sputter: the condition of preceding transparency conducting layer sputter is: target In
2O
3: SnO
2=90: 10, Ar throughput 400Sccm and O
2Throughput 0.6Sccm; Sputtering power is 0.30～0.75kW, and pressure is 0.65～0.85Pa, and temperature is 205～225 ℃; The oxygen of trace can change the crystalline state of film in the sputter procedure, reduces resistivity.
3, Cement Composite Treated by Plasma: the condition of Cement Composite Treated by Plasma is: pressure 165～175Pa, and power 500W, 225～235 ℃ of temperature, hydrogen or nitrogen fluoride 100%, Cement Composite Treated by Plasma 4min forms suede structure.
4, PECVD successive sedimentation p-a-Si:H film-amorphous silicon film or microcrystalline sillicon film: PECVD is a plasma reinforced chemical vapour deposition;
The condition of PECVD deposition p-a-Si:H film is: the doping ratio that mixes borine is 30%, and the boron atom with coordination mode Cheng Jian, makes the boron atom become effective acceptor impurity in the a-Si:H network.Underlayer temperature is 225～255 ℃, and radio-frequency power 200～250W, gas are silane 60%, hydrogen 40%, borine 30%, and growth air pressure is 85～95Pa;
The condition of PECVD deposited amorphous silicon fiml or microcrystalline sillicon film is: 250～300 ℃ of underlayer temperatures, radio-frequency power 200～250W, gas silane 70% and hydrogen 50%, growth air pressure 65～75Pa.
5, micro etch is cleaned: the micro etch cleaning condition is: million cleanings, washing, IPA steam drying, the etching that adopt 1.6MHz.Etching agent is HF: NH
4F: H
2O=0.17: 17.10: 82.73, its effect was to remove the silica on the a-Si top layer of easy oxidation, in order to avoid loose contact; Want the control time shorter after substrate cleans, because surperficial that expose to the open air is a-Si:H, in air, parks and can reoxidize, the time was less than 20 minutes; Also do not carry out film forming like overtime, then need heavily wash.
6, vacuum evaporation dielectric layer lithium fluoride or spin coating method thin polymer film: the condition of vacuum evaporation dielectric layer lithium fluoride or spin coating method thin polymer film is: lithium fluoride adopts molybdenum boat, and temperature is 200 ℃, uses crystal oscillator monitoring evaporation rate to be per minute 1 lattice;
The condition of polymer is: adopt 3, the polymer and the poly styrene sulfonate of 4-enedioxy thiophene monomer increase current density; Spin speed is 3000rpm/60s, 130 ℃ of annealing 10 minutes under atmospheric condition after the spin coating, annealing back cooling 3 minutes.
7, continuous evaporating-plating back electrode Al: in the vacuum evaporation back electrode Al step, aluminium purity is 99.999%, and the vapor deposition electric current is 2A, uses crystal oscillator monitoring evaporation rate to be per minute 10 lattice, vapor deposition pressure 8 * 10
-3Pa.
8, after the processing, obtain finished product.
Embodiment 1: adopt the amorphous silicon membrane battery of the Schottky junction structure that has dielectric layer of technological process preparation as shown in table 1, the structure of the battery of gained is as shown in Figure 1.
Table 1
Table 2 is presented at the stationary value of testing under the reference condition: radiancy is 1000W/m
2, spectrum AM1.5; Temperature is 25 ℃.
Table 2
| Title | Embodiment 1 |
| Substrate size: | 635mm*1245mm*7mm |
| Cut size: | 100mm*100mm |
| The battery testing area: | 0.19625cm 2 |
| Firm power under the reference condition: | Wp＝1.24mW±5％ |
| Rated operational voltage: | 0.60V±5％ |
| Rated operational current: | 10.55mA/cm 2±5％ |
| Open circuit voltage: | 0.78V±5％ |
| Short circuit current: | 13.27mA/cm 2±5％ |
| Efficient: | 6.33％±5％ |
Embodiment 2:
Step 4 is PECVD deposition p-a-Si:H-microcrystal silicon μ c-Si:H.
Step 6 for the condition of polymer is: adopt 3, the polymer and the poly styrene sulfonate of 4-enedioxy thiophene monomer increase current density.Spin speed is 3000rpm/60s; 130 ℃ of annealing 10 minutes under atmospheric condition after the spin coating, annealing back cooling 3 minutes.Other step is with embodiment 1, and the structure of the battery of gained is as shown in Figure 2.
The amorphous silicon membrane cell photoelectric transformation efficiency of the Schottky junction structure that has dielectric layer of the embodiment of the invention 1 preparation is 6.33%.
Claims (8)
1. an amorphous silicon membrane battery that has the Schottky junction structure of dielectric layer is characterized in that: be the back of the body Schottky junction structure that has dielectric layer that is made up of from the bottom up transparent substrates (glass), preceding transparency conducting layer TCO, ohmic contact layer p-a-Si:H, absorbed layer (active layer) i-a-Si:H or microcrystal silicon i-μ c-Si:H, dielectric layer LiF or polymer, back electrode Al.
2. a kind of amorphous silicon membrane battery that has the Schottky junction structure of dielectric layer according to claim 1 is characterized in that: described transparent substrates adopts the glass of high transmission rate.
3. a kind of amorphous silicon membrane battery that has the Schottky junction structure of dielectric layer according to claim 1 is characterized in that: transparency conducting layer TCO adopts suede structure before described, and its thickness is 100nm.
4. a kind of amorphous silicon membrane battery that has the Schottky junction structure of dielectric layer according to claim 1 is characterized in that: described ohmic contact layer p-a-Si:H adopts p type amorphous silicon membrane, and its thickness is 20nm.
5. a kind of amorphous silicon membrane battery that has the Schottky junction structure of dielectric layer according to claim 1 is characterized in that: what described absorbed layer adopted is amorphous silicon or microcrystal silicon, and its thickness is 200～400nm.
6. a kind of amorphous silicon membrane battery that has the Schottky junction structure of dielectric layer according to claim 1 is characterized in that: what described dielectric layer adopted is lithium fluoride or polymer, and its thickness is 0.2～4nm.
7. a kind of amorphous silicon membrane battery that has the Schottky junction structure of dielectric layer according to claim 1 is characterized in that: described back electrode adopts the Al film, and its thickness is 50～100nm.
8. the manufacture method of the amorphous silicon membrane battery of a Schottky junction structure that has a dielectric layer, this method may further comprise the steps:
(1), transparent substrates is cleaned: scrub, use 0.3% surfactant; Washing, processing procedure is, preceding feedwater 10s, draining 30s, the 90s that feeds water, totally twice, the US ultrasonic cleaning, frequency of ultrasonic is 35KHz, Rotary drying;
(2), preceding transparency conducting layer sputter: the condition of preceding transparency conducting layer sputter is: target In
2O
3: SnO
2=90: 10, Ar throughput 400Sccm and O
2Throughput 0.6Sccm; Sputtering power is 0.30～0.75kW, and pressure is 0.65～0.85Pa, and temperature is 205～225 ℃; The oxygen of trace can change the crystalline state of film in the sputter procedure, reduces resistivity;
(3), Cement Composite Treated by Plasma: the condition of Cement Composite Treated by Plasma is: pressure 165～175Pa, power 500W, 225～235 ℃ of temperature, hydrogen or nitrogen fluoride 100%, Cement Composite Treated by Plasma 4min, formation suede structure;
(4), PECVD successive sedimentation p-a-Si:H film-amorphous silicon film or microcrystalline sillicon film: PECVD is a plasma reinforced chemical vapour deposition;
The condition of PECVD deposition p-a-Si:H film is: the doping ratio that mixes borine is 30%, and the boron atom with coordination mode Cheng Jian, makes the boron atom become effective acceptor impurity in the a-Si:H network.Underlayer temperature is 225～255 ℃, and radio-frequency power 200～250W, gas are silane 60%, hydrogen 40%, borine 30%, and growth air pressure is 85～95Pa;
The condition of PECVD deposited amorphous silicon fiml or microcrystalline sillicon film is: 250～300 ℃ of underlayer temperatures, radio-frequency power 200～250W, gas silane 70% and hydrogen 50%, growth air pressure 65～75Pa;
(5), micro etch is cleaned: the micro etch cleaning condition is: million cleanings, washing, IPA steam drying, the etching that adopt 1.6MHz.Etching agent is HF: NH
4F: H
2O=0.17: 17.10: 82.73, its effect was to remove the silica on the a-Si top layer of easy oxidation, in order to avoid loose contact; Want the control time shorter after substrate cleans, because surperficial that expose to the open air is a-Si:H, in air, parks and can reoxidize, the time was less than 20 minutes; Also do not carry out film forming like overtime, then need heavily wash;
(6), vacuum evaporation dielectric layer lithium fluoride or spin coating method thin polymer film: the condition of vacuum evaporation dielectric layer lithium fluoride or spin coating method thin polymer film is: lithium fluoride adopts molybdenum boat, and temperature is 200 ℃, uses crystal oscillator monitoring evaporation rate to be per minute 1 lattice;
The condition of polymer is: adopt 3, the polymer and the poly styrene sulfonate of 4-enedioxy thiophene monomer increase current density; Spin speed is 3000rpm/60s, 130 ℃ of annealing 10 minutes under atmospheric condition after the spin coating, annealing back cooling 3 minutes;
(7), continuous evaporating-plating back electrode Al: in the vacuum evaporation back electrode Al step, aluminium purity is 99.999%, and the vapor deposition electric current is 2A, uses crystal oscillator monitoring evaporation rate to be per minute 10 lattice, vapor deposition pressure 8 * 10
-3Pa;
(8), handle after, obtain finished product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985787A (en) * | 2014-05-20 | 2014-08-13 | 新奥光伏能源有限公司 | Texturing method of transparent conductive oxide thin film |
| CN108110070A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | The transparent silicon film solar batteries of TCO/p/i/TCO glass structures and its preparation |
| WO2019184576A1 (en) * | 2018-03-26 | 2019-10-03 | 赵博阳 | Solar cell |
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| US4200473A (en) * | 1979-03-12 | 1980-04-29 | Rca Corporation | Amorphous silicon Schottky barrier solar cells incorporating a thin insulating layer and a thin doped layer |
| WO2009095909A2 (en) * | 2008-01-28 | 2009-08-06 | Yeda Research And Development Company Ltd. | Solar cells |
| CN101820011A (en) * | 2009-12-24 | 2010-09-01 | 江苏华创光电科技有限公司 | Schottky thin-film solar cell |
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| US4200473A (en) * | 1979-03-12 | 1980-04-29 | Rca Corporation | Amorphous silicon Schottky barrier solar cells incorporating a thin insulating layer and a thin doped layer |
| WO2009095909A2 (en) * | 2008-01-28 | 2009-08-06 | Yeda Research And Development Company Ltd. | Solar cells |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985787A (en) * | 2014-05-20 | 2014-08-13 | 新奥光伏能源有限公司 | Texturing method of transparent conductive oxide thin film |
| CN108110070A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | The transparent silicon film solar batteries of TCO/p/i/TCO glass structures and its preparation |
| WO2019184576A1 (en) * | 2018-03-26 | 2019-10-03 | 赵博阳 | Solar cell |
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Application publication date: 20120502 |