CN102496647A - Amorphous silicon film cell additionally equipped with electrode modification layer and manufacturing method thereof - Google Patents
Amorphous silicon film cell additionally equipped with electrode modification layer and manufacturing method thereof Download PDFInfo
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- CN102496647A CN102496647A CN201110445841XA CN201110445841A CN102496647A CN 102496647 A CN102496647 A CN 102496647A CN 201110445841X A CN201110445841X A CN 201110445841XA CN 201110445841 A CN201110445841 A CN 201110445841A CN 102496647 A CN102496647 A CN 102496647A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an amorphous silicon film cell additionally equipped with an electrode modification layer and a manufacturing method thereof. The film cell comprises: a transparent substrate, a front transparent conductive layer, a first electrode modification layer, a first window layer, a second window layer, intrinsic amorphous silicon, n-type amorphous silicon, a second electrode modification layer and a back electrode aluminum film. Simultaneously, the invention also provides a manufacturing method of the film cell. The method comprises the following steps: cleaning the transparent substrate; depositing a TCO layer by using LPCVD; performing continuous vacuum film coating by using PECVD (the first electrode modification layer, the first window layer, the second window layer, the intrinsic amorphous silicon and the n-type amorphous silicon); cleaning and sputtering the electrode modification layer and the back electrode aluminum layer. A pin structure of the amorphous silicon film is used in the invention. An anode modification layer a-Ge:H and a cathode modification layer ZAO are additionally arranged. A double layer window layer is used simultaneously. Absorption of a sunlight spectrum in a short wave area and a long wave area can be increased. Absorption losses and a series resistance can be reduced. An open circuit voltage and a filling factor can be increased. By using a continuous film method, a technology is simple and 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 of setting up the electrode modification layer.
Background technology
Non-crystal silicon solar cell is because but large tracts of land, cost of manufacture is low and have good application prospects with current technical compatibility.In the research of amorphous silicon battery, cost and performance are the themes of current research, and for further raising the efficiency, people make up the lamination amorphous silicon battery, adopt two structures to a plurality of pin single junction cell serial or parallel connections to raise the efficiency.Increase cost of manufacture so beyond doubt, reduced production capacity.
General unijunction pin amorphous silicon battery is the successive sedimentation p on glass at nesa coating TCO
+-a-Si:H, i-a-Si:H, n
+-a-Si:H constitutes, and wherein the amorphous silicon membrane i-a-Si:H of intrinsic is that main light absorbing zone produces a large amount of photo-generated carriers, and n
+And p
+Doped layer does not produce photo-generated carrier basically.This unijunction hull cell technology is simple, but the photic deterioration of amorphous silicon material itself and Spectral matching property completely inadequately cause efficient and stability not good, have limited further developing of amorphous silicon membrane battery.Raise the efficiency, the method for enhanced stability generally is to adopt the material of low absorption of broad-band gap as Window layer, and the material that adopts high Spectral matching.
The carbon doped p is arranged
+The a-SiC:H layer has the band gap of broad, can be used as Window layer.The p of broad-band gap
+The a-SiC:H layer has reduced optical absorption loss, has strengthened the absorption of light at intrinsic layer, has improved short circuit current.But the p of broad-band gap
+The a-SiC:H layer has but increased p
+The anodic interface potential barrier of iC:H layer/tco layer reduces fill factor, curve factor.
Aluminium is owing to good conductivity, low being commonly used in of cost are done cathode material in the solar cell.But in the pin structure, there are negative electrode Al and n too
+The problem that photo-generated carrier is derived between the a-Si:H layer causes series resistance big, and fill factor, curve factor is low.
In this case, on the basis of how to realize raising the efficiency, simplify technology, improve production capacity; How can in unijunction pin structure, utilize the p of broad-band gap
+The a-SiC:H layer increases the utilance of sunlight, can add one again and have appropriate bandgap width and work function matched materials as the anodic interface decorative layer, reduces series resistance and strengthens the collection of anode photo-generated carrier; And the potential barrier that how can reduce cathode interface promotes the derivation of photo-generated carrier, can compensate the deficiency of amorphous silicon Spectral matching again, strengthens shortwave and long wave Spectral matching; These all are problem demanding prompt solutions.
Summary of the invention
The objective of the invention is in order to solve in the above-mentioned existing unijunction pin structure, the problem that the spectrum utilance is not high, series resistance is big that amorphous silicon thin-film solar cell exists, and a kind of amorphous silicon membrane battery and manufacture method of setting up the electrode modification layer is provided.
The present invention's the amorphous silicon membrane battery of setting up the electrode modification layer is by transparent substrates, preceding transparency conducting layer TCO, the first electrode modification layer a-Ge:H, the first Window layer p
+-μ the c-Si:H and the second Window layer p
+The amorphous silicon membrane battery of setting up the electrode modification layer that-a-SiC:H, intrinsic amorphous silicon i-a-Si:H, n type amorphous silicon n-a-Si:H, the second electrode modification layer ZAO, back electrode aluminium film Al constitute from the bottom up.
Described transparent substrates adopts the glass or the flexible substrate of high transmission rate.
Transparency conducting layer TCO adopts the zinc oxide ZnO:B of boron-doping before described, and forms suede structure, and light passes by battery from it and absorbs, and serves as the electrode of battery again, requires transmitance height, good conductivity, adopts the method preparation of low-pressure chemical vapor deposition (LPCVD).Its thickness is 1000～2000nm.
The described first electrode modification layer adopts amorphous germanium a-Ge:H, with the preparation of plasma reinforced chemical vapour deposition (PECVD) method, adopts GeH
4Transparency conducting layer TCO surface forms thin film before handling, and the modified anode interface reduces the anodic interface potential barrier, and its thickness is 2～10nm.
Described first Window layer adopts p type microcrystal silicon p
+-μ c-Si:H as the window ground floor, increases Spectral matching property and stability, and its thickness is 2～20nm.
Described second Window layer adopts p type noncrystalline silicon carbide p
+-a-SiC:H as the window second layer, utilizes broad-band gap to reduce optical absorption loss, improves short circuit current, and its thickness is 10～30nm.
That described intrinsic amorphous silicon is that absorbed layer adopts is amorphous silicon i-a-Si:H, and as light absorbing zone, its thickness is 200～400nm.
N type amorphous silicon in the described pin structure adopts amorphous silicon n
+-a-Si:H, its thickness 10～30nm.
That the described second electrode modification layer adopts is the zinc-oxide film ZAO that mixes aluminium, adopts sputtering method to form the embellishing cathode interface layer, is used to improve light utilization efficiency, and reduces the cathode interface potential barrier, protects battery simultaneously, and its thickness is 0.2～30nm.
Described back electrode film adopts the aluminium film, adopts the method for continuous sputter, improves production capacity, and its thickness is 50～200nm.
The manufacture method of the present invention's the amorphous silicon membrane battery of setting up the electrode modification layer 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, ultrasonic cleaning, frequency of ultrasonic is 35KHz, Rotary drying;
2, the preceding transparency conducting layer of low-pressure chemical vapor deposition (LPCVD) (TCO): preceding transparency conducting layer adopts the zinc oxide ZnO:B of boron-doping, diethyl zinc (C
2H
5)
2The Zn flow is that 10～15sccm and water vapor concentration flow are 12～20sccm, the B of doping
2H
6Concentration is 0.1～3%, and reaction pressure is 10～80Pa, and temperature is 100～400 ℃.
3, plasma reinforced chemical vapour deposition (PECVD) continuous vacuum coating: the first electrode modification layer a-Ge:H, adopt germane GeH
4Concentration 100%, pressure 150～180Pa, power 100～500W, 100～260 ℃ of temperature, Cement Composite Treated by Plasma 2～20min;
The first Window layer p
+-μ c-Si:H adopts borine B
2H
6, silane SiH
4, hydrogen H
2, high hydrogen thinner ratio H
2/ SiH
4=50～400, B
2H
6/ SiH
4=0.1～4, temperature is 110～260 ℃, power 100～260W;
The second Window layer p
+-a-SiC:H adopts silane SiH
4Concentration is 30～70%, hydrogen H
2Concentration is 20～50%, borine B
2H
6Concentration is 20～80%, methane CH
4Concentration is 10～70%, and temperature is 100～260 ℃, power 100～260W;
Intrinsic amorphous silicon i-a-Si:H adopts silane SiH
4Concentration is 70%, hydrogen H
2Concentration is 50%, 180～260 ℃ of underlayer temperatures, radio-frequency power 200～250W, growth air pressure 65～75Pa;
N type amorphous silicon n
+-a-Si:H adopts silane SiH
4Concentration is 40%, hydrogen H
2Concentration is 40%, phosphorus PH
3Concentration is 60%, 200～260 ℃ of underlayer temperatures, radio-frequency power 200～250W, growth air pressure 60～130Pa;
4, micro etch is cleaned: the micro etch cleaning condition is: million cleanings, circulation washing, micro etch, the ozone O that adopt 1.6MHz
3Water cleans, ultrasonic cleaning, and isopropyl alcohol is dry.Microetch is HF: NH
4F: H
2O=0.17: 17.10: 82.73, its effect was n
+The silica on a-Si top layer removes, in order to avoid O is used in loose contact again
3Surface after when water cleans forms the thin silica of one deck; After cleaning, substrate want the control time shorter, because surperficial that expose to the open air is n
+A-Si:H parks in air and can reoxidize, and the time was less than 20 minutes; Also do not carry out film forming like overtime, then need heavily wash;
5, the zinc-oxide film ZnO:Al of aluminium is mixed in sputter: base vacuum 10
-5Pa, argon flow amount are 10～60sccm, and sputtering pressure is 0.2～4.0Pa, and power is 10～200W, and temperature is room temperature～150 ℃, magnetic scanning number of times 1～5scan;
6, continuous sputter back electrode Al: the argon Ar flow is 40～60sccm, and sputtering pressure is 0.2～2.0Pa, and power is 1～10kW, and temperature is 220～260 ℃, magnetic scanning number of times 1～5scan;
7, after the processing, obtain finished product.
Description of drawings
Fig. 1 is the structural representation of the present invention's the amorphous silicon membrane battery of setting up the electrode modification layer.
Fig. 2 is the photoelectric characteristic sketch map of the present invention to the amorphous silicon membrane battery of setting up the electrode modification layer.
Embodiment
As shown in Figure 1, the present invention's the amorphous silicon membrane battery of setting up the electrode modification layer is by transparent substrates, preceding transparency conducting layer TCO, the first electrode modification layer a-Ge:H, the first Window layer p
+-μ the c-Si:H and the second Window layer p
+-a-SiC:H, intrinsic amorphous silicon i-a-Si:H, n type amorphous silicon n
+The amorphous silicon membrane battery of setting up the electrode modification layer that-a-Si:H, the second electrode modification layer ZAO, back electrode film Al constitute from the bottom up.
Described transparent substrates adopts the glass or the flexible substrate of high transmission rate.
Transparency conducting layer TCO adopts the zinc oxide ZnO:B of boron-doping before described, and forms suede structure, and light passes by battery from it and absorbs, and serves as the electrode of battery again, requires transmitance height, good conductivity, adopts the method preparation of low-pressure chemical vapor deposition (LPCVD).Its thickness is 1000～2000nm.
The described first electrode modification layer adopts amorphous germanium a-Ge:H, with the preparation of plasma reinforced chemical vapour deposition (PECVD) method, adopts GeH
4Handle the TCO surface, form thin film, the modified anode interface reduces the anodic interface potential barrier, and its thickness is 2～10nm.
Described first Window layer adopts p type microcrystal silicon p
+-μ c-Si:H as the window ground floor, increases Spectral matching property and stability, and its thickness is 2～20nm.
Described second Window layer adopts p type noncrystalline silicon carbide p
+-a-SiC:H as the window second layer, utilizes broad-band gap to reduce optical absorption loss, improves short circuit current, and its thickness is 10～30nm.
That described intrinsic amorphous silicon is that absorbed layer adopts is amorphous silicon i-a-Si:H, and as light absorbing zone, its thickness is 200～400nm.
N type in the described pin structure adopts amorphous silicon n
+-a-Si:H, its thickness 10～30nm.
That the described second electrode modification layer adopts is the zinc-oxide film ZAO that mixes aluminium, adopts sputtering method to form the embellishing cathode interface layer, is used to improve light utilization efficiency, and reduces the cathode interface potential barrier, protects battery simultaneously, and its thickness is 0.2～30nm.
Described back electrode adopts aluminium (Al) film, adopts the method for continuous sputter, improves production capacity, and its thickness is 50～200nm.
The manufacture method of the present invention's the amorphous silicon membrane battery of setting up the electrode modification layer 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, ultrasonic cleaning, frequency of ultrasonic is 35KHz, Rotary drying;
2, the preceding transparency conducting layer of low-pressure chemical vapor deposition (LPCVD) (TCO): preceding transparency conducting layer adopts the zinc oxide ZnO:B of boron-doping, diethyl zinc (C
2H
5)
2The Zn flow is that 10～15sccm and water vapor concentration flow are 12～20sccm, the B of doping
2H
6Concentration is 0.1～3%, and reaction pressure is 10～80Pa, and temperature is 100～400 ℃.
3, plasma reinforced chemical vapour deposition (PECVD) continuous vacuum coating: electrode modification layer a-Ge:H, adopt germane GeH
4Concentration 100%, pressure 150～180Pa, power 100～500W, 100～260 ℃ of temperature, Cement Composite Treated by Plasma 2～20min;
The first Window layer p
+-μ c-Si:H adopts borine B
2H
6, silane SiH
4, hydrogen H
2, high hydrogen thinner ratio H
2/ SiH
4=50～400, B
2H
6/ SiH
4=0.1～4, temperature is 110～260 ℃, power 100～260W;
The second Window layer p
+-a-SiC:H adopts silane SiH
4Concentration is 30～70%, hydrogen H
2Concentration is 20～50%, borine B
2H
6Concentration is 20～80%, methane CH
4Concentration is 10～70%, and temperature is 100～260 ℃, power 100～260W;
Intrinsic amorphous silicon i-a-Si:H adopts silane SiH
4Concentration is 70%, hydrogen H
2Concentration is 50%, 180～260 ℃ of underlayer temperatures, radio-frequency power 200～250W, growth air pressure 65～75Pa;
N type amorphous silicon n
+-a-Si:H adopts silane SiH
4Concentration is 40%, hydrogen H
2Concentration is 40%, phosphorus PH
3Concentration is 60%, 200～260 ℃ of underlayer temperatures, radio-frequency power 200～250W, growth air pressure 60～130Pa;
4, micro etch is cleaned: the micro etch cleaning condition is: million cleanings, circulation washing, micro etch, the ozone O that adopt 1.6MHz
3Water cleans, ultrasonic cleaning, and isopropyl alcohol is dry.Microetch is HF: NH
4F: H
2O=0.17: 17.10: 82.73, its effect was n
+The silica on a-Si top layer removes, in order to avoid O is used in loose contact again
3Surface after when water cleans forms the thin silica of one deck; After cleaning, substrate want the control time shorter, because surperficial that expose to the open air is n
+A-Si:H parks in air and can reoxidize, and the time was less than 20 minutes; Also do not carry out film forming like overtime, then need heavily wash;
5, the zinc-oxide film ZnO:Al of aluminium is mixed in sputter: base vacuum 10
-5Pa, argon flow amount are 10～60sccm, and sputtering pressure is 0.2～4.0Pa, and power is 10～200W, and temperature is room temperature～150 ℃, magnetic scanning number of times 1～5scan;
6, continuous sputter back electrode Al: the argon Ar flow is 40～60sccm, and sputtering pressure is 0.2～2.0Pa, and power is 1～10kW, and temperature is 220～260 ℃, magnetic scanning number of times 1～5scan;
7, after the processing, obtain finished product.
Adopt the photoelectric characteristic of the amorphous silicon membrane battery of setting up the electrode modification layer of this technological process preparation as shown in Figure 2.
Table 1 is presented at the stationary value of testing under the reference condition: radiancy is 1000W/m
2, spectrum AM1.5; Temperature is 25 ℃.
Table 1
| 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＝1.62mW±5％ |
| Rated operational voltage: | 0.66V±5％ |
| Rated operational current: | 12.48mA/cm 2±5％ |
| Open circuit voltage: | 0.9V±5％ |
| Short circuit current: | 15.63mA/cm 2±5％ |
| Efficient: | 8.26％±5％ |
Table 2 is the photoelectric properties parameter of the amorphous silicon membrane battery of setting up the electrode modification layer of this technological process preparation of employing.
Table 2
Claims (10)
1. an amorphous silicon membrane battery of setting up the electrode modification layer is characterized in that: be by transparent substrates, preceding transparency conducting layer TCO, the first electrode modification layer a-Ge:H, the first Window layer p
+I:H, the second Window layer p
+-a-SiC:H, intrinsic amorphous silicon i-a-Si:H, n type amorphous silicon n
+-a-Si:H, the second electrode modification layer ZAO and back electrode aluminium Al constitute from the bottom up.
2. a kind of amorphous silicon membrane battery of setting up the electrode modification layer according to claim 1 is characterized in that: transparency conducting layer adopts the zinc oxide of boron-doping before described, and forms suede structure, and its thickness is 1000～2000nm.
3. a kind of amorphous silicon membrane battery of setting up the electrode modification layer according to claim 1 is characterized in that: the described first electrode modification layer adopts amorphous germanium a-Ge:H, and its thickness is 2～10nm.
4. a kind of amorphous silicon membrane battery of setting up the electrode modification layer according to claim 1 is characterized in that: described first Window layer adopts p type microcrystal silicon p
+-μ c-Si:H, its thickness are 2～20nm.
5. a kind of amorphous silicon membrane battery of setting up the electrode modification layer according to claim 1 is characterized in that: described second Window layer adopts p type noncrystalline silicon carbide p
+-a-SiC:H, its thickness are 10～30nm.
6. a kind of amorphous silicon membrane battery of setting up the electrode modification layer according to claim 1 is characterized in that: that described intrinsic amorphous silicon is that absorbed layer adopts is amorphous silicon i-a-Si:H, and its thickness is 200～400nm.
7. a kind of amorphous silicon membrane battery of setting up the electrode modification layer according to claim 1 is characterized in that: the n type amorphous silicon in the described pin structure adopts amorphous silicon n
+I:H, its thickness 10～30nm.
8. a kind of amorphous silicon membrane battery of setting up the electrode modification layer according to claim 1 is characterized in that: what the described second electrode modification layer adopted is the zinc-oxide film of mixing aluminium, and its thickness is 0.2～30nm.
9. a kind of amorphous silicon membrane battery of setting up the electrode modification layer according to claim 1 is characterized in that: described back electrode adopts the aluminium Al film of sputter, and its thickness is 50～200nm.
10. manufacture method of setting up the amorphous silicon membrane battery of electrode modification 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, ultrasonic cleaning, frequency of ultrasonic is 35KHz, Rotary drying;
(2), the preceding transparency conducting layer of low-pressure chemical vapor deposition (LPCVD) (TCO): preceding transparency conducting layer adopts the zinc oxide ZnO:B of boron-doping, diethyl zinc (C
2H
5)
2The Zn flow is that 10～15sccm and water vapor concentration flow are 12～20sccm, the B of doping
2H
6Concentration is 0.1～3%, and reaction pressure is 10～80Pa, and temperature is 100～400 ℃;
(3), plasma reinforced chemical vapour deposition (PECVD) continuous vacuum coating: the first electrode modification layer a-Ge:H, employing germane GeH
4Concentration 100%, pressure 150～180Pa, power 100～500W, 100～260 ℃ of temperature, Cement Composite Treated by Plasma 2～20min;
The first Window layer p
+-μ c-Si:H adopts borine B
2H
6, silane SiH
4, hydrogen H
2, high hydrogen thinner ratio H
2/ SiH
4=50～400, B
2H
6/ SiH
4=0.1～4, temperature is 110～260 ℃, power 100～260W;
The second Window layer p
+-a-SiC:H adopts silane SiH
4Concentration is 30～70%, hydrogen H
2Concentration is 20～50%, borine B
2H
6Concentration is 20～80%, methane CH
4Concentration is 10～70%, and temperature is 100～260 ℃, power 100～260W;
Intrinsic amorphous silicon i-a-Si:H adopts silane SiH
4Concentration is 70%, hydrogen H
2Concentration is 50%, 180～260 ℃ of underlayer temperatures, radio-frequency power 200～250W, growth air pressure 65～75Pa;
N type amorphous silicon n
+-a-Si:H adopts silane SiH
4Concentration is 40%, hydrogen H
2Concentration is 40%, phosphorus PH
3Concentration is 60%, 200～260 ℃ of underlayer temperatures, radio-frequency power 200～250W, growth air pressure 60～130Pa;
(4), micro etch is cleaned: the micro etch cleaning condition is: million cleanings, circulation washing, micro etch, the ozone O that adopt 1.6MHz
3Water cleans, ultrasonic cleaning, and isopropyl alcohol is dry; Microetch is HF: NH
4F: H
2O=0.17: 17.10: 82.73, use ozone O again
3Water cleans, and the open-assembly time after the cleaning was less than 20 minutes; Also do not carry out film forming like overtime, then need heavily wash;
(5), the zinc-oxide film ZnO:Al of aluminium is mixed in sputter: base vacuum 10
-5Pa, argon flow amount are 10～60sccm, and sputtering pressure is 0.2～4.0Pa, and power is 10～200W, and temperature is room temperature～150 ℃, magnetic scanning number of times 1～5scan;
(6), continuous sputter back electrode aluminium Al: the argon Ar flow is 40～60sccm, and sputtering pressure is 0.2～2.0Pa, and power is 1～10kW, and temperature is 220～260 ℃, magnetic scanning number of times 1～5scan.
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Application publication date: 20120613 |