CN102324448B - The preparation method of InGaN solar cell is tied in a kind of upside-down mounting three - Google Patents
The preparation method of InGaN solar cell is tied in a kind of upside-down mounting three Download PDFInfo
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- CN102324448B CN102324448B CN201110281968.2A CN201110281968A CN102324448B CN 102324448 B CN102324448 B CN 102324448B CN 201110281968 A CN201110281968 A CN 201110281968A CN 102324448 B CN102324448 B CN 102324448B
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Abstract
The present invention relates to the preparation method that InGaN solar cell is tied in a kind of upside-down mounting three, comprise the following steps: (1) evaporation reflector on carrier, reflector sputters two metal salient points; (2) substrate generates successively GaN nucleating layer, GaN resilient coating, an InGaN battery, the first tunnel junction, the 2nd InGaN battery, the second tunnel junction, the 3rd InGaN battery, cap layers, translucent current extending; (3) first time photoetching; (4) dry etching; (5) second time photoetching; (6) positive and negative electrode evaporation, forms solar cell device; By step (6) in positive and negative electrode and step (1) in two metal salient point bondings.The present invention adopts inverted structure, cap layers, the metal salient point of bonding between carrier and positive and negative electrode, fully absorb solar spectrum, external quantum efficiency is more than 70%, improve photoelectric conversion efficiency, extend the useful life of battery, strengthen battery operated stability, and can be used as complete battery and directly apply.
Description
Technical field
The invention belongs to solar battery structure technical field, particularly relate to the preparation method that InGaN solar cell is tied in a kind of upside-down mounting three.
Background technology
The known energy is all non-renewable, after exploitation for many years, the reserves of these energy are all reducing day by day, and serious environmental problem can be caused after using, so people more and more pay attention to this inexhaustible green energy resource of solar energy, for a long time, all at the material finding high conversion efficiency diligently.In recent years, be that the third generation semi-conducting material of representative---III group-III nitride is the focus that people study with GaN and InGaN, AlGaN, it is mainly used in photoelectric device and high temperature, high frequency, high power device.The result of study of 2002 shows, the energy gap of InN be not before the 1.89eV of report but 0.7eV, this just means by regulating In component in InGaN material, can make its energy gap from 3.4eV (GaN) to 0.7eV (InN) continuously adjustabe, namely the wavelength of its corresponding absorption spectrum can extend to near-infrared part (1770nm) from ultraviolet portion (365nm), almost intactly cover whole solar spectrum, in addition, also have absorption coefficient high, electron mobility is high, the advantages such as capability of resistance to radiation is strong, so the application of InGaN material in area of solar cell causes the close attention of people.
The development trend of InGaN solar cell is that series-connected solar cells is tied in preparation more, this is because its energy gap is continuously adjustable in the main scope of solar spectrum, be easy to the material obtaining band gap corresponding with theoretical maximum conversion efficiency, and when battery footing is increased to more, this advantage can be more obvious.Theory calculate shows, the highest theoretical conversion efficiencies of InGaN binode and three-joint solar cell all higher than the solar cell of existing traditional material at present, such as GaInP/GaAs binode battery, the theoretical value of GaInP/GaAs/Ge tri-junction battery.But can not grow by forward as traditional material in actual growth course, this is because the growth temperature of InGaN material increases along with the minimizing of In content, if can spread by the method for forward growth, thus affect the performance of solar cell, so back growth the method for upside-down mounting makes InGaN many knots series-connected solar cells become possibility.
Find that the patent No. is 200710120608.8 through retrieval, name is called: the patent of invention of upside-down mounting binode In-Ga-N solar battery structure, and structure comprises a substrate, it is followed successively by a low temperature nitride gallium nucleating layer, one unintentionally doped gallium nitride resilient coating, a N-shaped doping In
aga
1-an layer, a p-type doping In
aga
1-an layer, a p-type heavy doping In
bga
1-bn layer, a N-shaped heavy doping In
bga
1-bn layer, a N-shaped doping In
cga
1-cn layer, a p-type doping In
cga
1-cn layer.This patent of invention solves and grow the comparatively difficult problem of low indium component indium gallium nitrogen on high indium component indium gallium nitrogen, its theoretical conversion efficiencies is by generally acknowledging that 41.3% brings up to 50% at present, but it is on the low side that technique scheme ties above battery efficiency relative to three knots or three, and the growth course described to InGaN material, directly cannot apply as complete solar cell, the preparation after InGaN Material growth process produces a very large impact to the performance of solar cell.
Summary of the invention
The present invention solves in known technology the technical problem existed to propose that a kind of external quantum efficiency is high, photoelectric conversion efficiency is high, long service life, cell working stability are high, and can be used as the preparation method that InGaN solar cell is tied in the direct applied upside-down mounting three of complete battery.
The technical scheme that the present invention takes for the technical problem existed in solution known technology is:
A preparation method for InGaN solar cell is tied in upside-down mounting three, is characterized in comprising the following steps:
(1) evaporation reflector on carrier, and two metal salient points are sputtered on reflector;
(2) by metal organic chemical vapor deposition, growing GaN nucleating layer, GaN resilient coating, an InGaN battery, the first tunnel junction, the 2nd InGaN battery, the second tunnel junction, the 3rd InGaN battery, cap layers successively on substrate; Then the translucent current extending of evaporation in cap layers;
(3) first time photoetching: make protection zone and etching region on translucent current extending by lithography;
(4) dry etching: by dry etching, remove step (3) in the translucent current extending of etching region, cap layers, the 3rd InGaN battery, the second tunnel junction, the 2nd InGaN battery, the first tunnel junction, an InGaN battery p-In
aga
1-an layer;
(5) second time photoetching: step (3) in protection zone translucent current extending on make positive electrode area by lithography, step (4) in the n-In of an InGaN battery
aga
1-an layer carves negative electrode area;
(6) electrode evaporation: step (5) in positive electrode area and negative electrode area respectively evaporation positive electrode and negative electrode, form solar cell device;
By step (6) in solar cell device be inverted, and by its positive electrode and negative electrode alignment procedures (1) in two metal salient point bondings.
The present invention can also take following technical scheme:
Described step (1) in carrier be Si, the reflector of evaporation on Si be 200nm Al and Al on the SiO of 80nm
2; The metal salient point sputtered on reflector is Au.
Described step (2) in the one InGaN battery Si adulterate n-In
aga
1-athe p-In of N layer and Mg doping
aga
1-an layer, wherein 0.45≤a≤0.65, doping content is 1 × 10
17-1 × 10
19cm
-3, thickness range is 100nm-300nm; The n-In that described 2nd InGaN battery Si adulterates
bga
1-bthe p-In of N layer and Mg doping
bga
1-bn layer, wherein 0.65≤b≤0.85, doping content is 1 × 10
17-1 × 10
19cm
-3, thickness range is 100nm-300nm; The n-In that described 3rd InGaN battery Si adulterates
cga
1-cthe p-In of N layer and Mg doping
cga
1-cn layer, wherein 0.85≤c≤1, doping content is 1 × 10
17-1 × 10
19cm
-3, thickness range is 100nm-300nm.
Described step (2) in the first tunnel junction comprise Si doping n
+-In
aga
1-athe p of N layer and Mg doping
+-In
aga
1-an layer, wherein 0.45≤a≤0.65, doping content is 1 × 10
19-1 × 10
20cm
-3, thickness range is 10nm-50nm; Described second tunnel junction, comprises the n of Si doping
+-In
bga
1-bthe p of N layer and Mg doping
+-In
bga
1-bn layer, wherein 0.65≤b≤0.85, doping content is 1 × 10
19-1 × 10
20cm
-3, thickness range is 10nm-50nm.
Described step (2) middle cap layers is the p of Mg doping
+-In
cga
1-cn, wherein 0.85≤c≤1, doping content is 1 × 10
19-1 × 10
20cm
-3, thickness range is 10nm-100nm.
Described step (2) in translucent current extending be ito film.
Described step (7) in negative electrode be the Ti/Al/Ti/Au of thickness 10/30/10/200nm from top to bottom, it is the n that adulterates in an InGaN battery Si of Ti evaporation at the middle and upper levels
+-In
aga
1-aunder N layer.
Described step (7) middle positive electrode is the Ni of thickness 30nm and the Au of thickness 80nm from top to bottom.
The advantage that the present invention has and good effect are:
1, the present invention adopts the preparation after solar cell device upside down and InGaN Material growth process, and fully absorb solar spectrum, external quantum efficiency is more than 70%, and theoretical conversion efficiencies can reach more than 55%, and can be used as complete battery and directly apply.
2, the present invention adopts heavily doped layer as cap layers, is conducive to realizing ohmic contact, and the translucent current extending of evaporation, further enhances the collection to charge carrier in addition, thus improves the conversion efficiency of battery.
3, the present invention adopts metal salient point and plays the carrier of mechanical support effect, improves the mechanical strength of battery, improves the successful probability of bonding, thus extends the useful life of battery, strengthen battery operated stability.
Accompanying drawing explanation
Fig. 1 is preparation method's structural representation that InGaN solar cell is tied in a kind of upside-down mounting three of the present invention.
Fig. 2 is the schematic top plan view after the present invention's first time photoetching;
Fig. 3 is the schematic top plan view after the photoetching of the present invention's second time.
In figure: 1, substrate; 2, GaN nucleating layer; 3, GaN resilient coating; 4, an InGaN battery; 5, the first tunnel junction; 6, the 2nd InGaN battery; 7, the second tunnel junction; 8, the 3rd InGaN battery; 9, cap layers; 10, translucent current extending; 11, positive electrode; 12, negative electrode; 13, metal salient point; 14, reflector; 15, carrier; 16, etching region; 17, protection zone; 18, positive electrode area; 19, negative electrode area.
Embodiment
For technology contents of the present invention, Characteristic can be understood further, hereby exemplify following examples, and coordinate accompanying drawing to be described in detail as follows:
Accompanying drawings 1-Fig. 3.
Select Si as carrier 15, adopt known evaporation process at the Al of first evaporation a layer thickness 200nm, then the SiO of evaporation a layer thickness 80nm
2, form the reflector 14 shown in Fig. 1, adopt known magnetically controlled sputter method on the reflector of carrier, to sputter 2 Au as metal salient point 13;
By Sapphire Substrate 1 annealing after 10 minutes under the condition of hydrogen and 1100 DEG C, adopt MOCVD and metal organic chemical vapor deposition technology face growing GaN nucleating layer 2, GaN resilient coating 3, InGaN battery 4, first tunnel junction 5, the 2nd InGaN battery 6, second tunnel junction 7, the 3rd InGaN battery 8, cap layers 9 successively on a sapphire substrate, concrete preparation process is:
GaN nucleating layer, growth temperature is 500 – 650 DEG C, and thickness range is 10-40nm, and this layer can increase the nucleation density of substrate surface;
GaN resilient coating, growth temperature is 950 – 1100 DEG C, and thickness range is 1-3 μm, and this layer can reduce the defect concentration of epitaxial loayer, thus improves crystal mass;
One InGaN battery, comprises the n-In of Si doping
aga
1-athe p-In of N layer and Mg doping
aga
1-an layer, wherein 0.45≤a≤0.65, growth temperature is 600 – 1000 DEG C, and doping content is 1 × 10
17-1 × 10
19cm
-3, thickness range is 100nm-300nm;
First tunnel junction, comprises the n of Si doping
+-In
aga
1-athe p of N layer and Mg doping
+-In
aga
1-an layer, wherein 0.45≤a≤0.65, growth temperature is 600 – 1000 DEG C, and doping content is 1 × 10
19-1 × 10
20cm
-3, thickness range is 10nm-50nm;
2nd InGaN battery, comprises the n-In of Si doping
bga
1-bthe p-In of N layer and Mg doping
bga
1-bn layer, wherein 0.65≤b≤0.85, growth temperature is 600 – 1000 DEG C, and doping content is 1 × 10
17-1 × 10
19cm
-3, thickness range is 100nm-300nm;
Second tunnel junction, comprises the n of Si doping
+-In
bga
1-bthe p of N layer and Mg doping
+-In
bga
1-bn layer, wherein 0.65≤b≤0.85, growth temperature is 600 – 1000 DEG C, and doping content is 1 × 10
19-1 × 10
20cm
-3, thickness range is 10nm-50nm;
3rd InGaN battery, comprises the n-In of Si doping
cga
1-cthe p-In of N layer and Mg doping
cga
1-cn layer, wherein 0.85≤c≤1, growth temperature is 600 – 1000 DEG C, and doping content is 1 × 10
17-1 × 10
19cm
-3, thickness range is 100nm-300nm;
Cap layers is the p of Mg doping
+-In
cga
1-cn layer, wherein 0.85≤c≤1, growth temperature is 600 – 1000 DEG C, and doping content is 1 × 10
19-1 × 10
20cm
-3, thickness range is 10nm-100nm.
The total time of above-mentioned layers of material growth is 5-7 hour, afterwards in cap layers evaporation ito film as translucent current extending 10, carry out first time photoetching, dry etching, second time photoetching, evaporation positive electrode 11 and negative electrode 12 more successively, form solar cell device, then solar cell device is inverted, be bonded to evaporation to have on the carrier 15 in reflector, preparation process is as follows:
Evaporation ITO: adopt known evaporation process evaporation ito film.For keeping the chemistry of ito thin film more unbalance than not, during evaporation, vacuum degree is 10
-4below Pa, through-current capacity is about the oxygen of 3.5sccm simultaneously, and the evaporation time is 1.5-2.5 hour, forms the translucent current extending of thickness 100-300nm, is placed on the N of 450 DEG C afterwards
2under environment, anneal 15 minutes;
First time photoetching: adopt known photoetching process, make the protection zone 17 shown in Fig. 2 and etching region 16 by lithography;
Dry etching: adopt known dry method etch technology, removes the p-In of the translucent current extending of etching region, cap layers, the 3rd InGaN battery, the second tunnel junction, the 2nd InGaN battery, the first tunnel junction, an InGaN battery
aga
1-an layer;
Second time photoetching: adopt known photoetching process, the translucent current extending of protection zone carves the positive electrode area 18 shown in Fig. 3, the n-In of the one InGaN battery in etching region
aga
1-an layer carves the negative electrode area 19 shown in Fig. 3;
Evaporation positive electrode: the Ni adopting known evaporation process first evaporation a layer thickness 30nm in positive electrode area, then the Au of evaporation a layer thickness 80nm, altogether evaporation 1.5-2.5 hour, form the positive electrode shown in Fig. 1; Vacuum degree during evaporation is 10
-4below Pa, finally at the N of 500 DEG C
2under environment, anneal 1 minute;
Evaporation negative electrode: adopt known evaporation process to be the Ti/Al/Ti/Au of 10/30/10/200nm in negative electrode area successively evaporation thickness, altogether evaporation 1.5-2.5 hour, form the negative electrode shown in Fig. 1; Vacuum degree during evaporation will be 10
-4below Pa, finally at the N of 800 DEG C
2under environment, anneal 3 minutes, form solar cell device.
Bonding: then the solar cell device prepared is inverted, and its positive electrode and negative electrode are aimed at metal salient point, adopt known bonding technology bonding 10-40 minute under 100-800 DEG C and 1.5-3.5 atmospheric pressure.
By the enforcement of above step, complete the preparation process that the preparation method of InGaN solar cell is tied in upside-down mounting three of the present invention.
Be more than the detailed description to the present invention one specific embodiment, this case protection range do not constituted any limitation that the technical method that all employing equivalents or equivalence are replaced and formed all drops within rights protection scope of the present invention.
Claims (8)
1. a preparation method for InGaN solar cell is tied in upside-down mounting three, it is characterized in that comprising the following steps:
(1) evaporation reflector on carrier, and two metal salient points are sputtered on reflector;
(2) by metal organic chemical vapor deposition, growing GaN nucleating layer, GaN resilient coating, an InGaN battery, the first tunnel junction, the 2nd InGaN battery, the second tunnel junction, the 3rd InGaN battery, cap layers successively on substrate; Then the translucent current extending of evaporation in cap layers;
(3) first time photoetching: make protection zone and etching region on translucent current extending by lithography;
(4) dry etching: by dry etching, remove step (3) in the translucent current extending of etching region, cap layers, the 3rd InGaN battery, the second tunnel junction, the 2nd InGaN battery, the first tunnel junction, an InGaN battery p-In
aga
1-an layer;
(5) second time photoetching: step (3) in protection zone translucent current extending on make positive electrode area by lithography, step (4) in the n-In of an InGaN battery
aga
1-an layer carves negative electrode area;
(6) electrode evaporation: step (5) in positive electrode area and negative electrode area respectively evaporation positive electrode and negative electrode, form solar cell device;
By step (6) in solar cell device be inverted, and by its positive electrode and negative electrode alignment procedures (1) in two metal salient point bondings.
2. the preparation method of InGaN solar cell is tied in upside-down mounting three according to claim 1, it is characterized in that: described step (1) in carrier be Si, the reflector of evaporation on Si be 200nm Al and Al on the SiO of 80nm
2; The metal salient point sputtered on reflector is Au.
3. the preparation method of InGaN solar cell is tied in upside-down mounting three according to claim 1, it is characterized in that: described step (2) in the one InGaN battery Si adulterate n-In
aga
1-athe p-In of N layer and Mg doping
aga
1-an layer, wherein 0.45≤a≤0.65, doping content is 1 × 10
17-1 × 10
19cm
-3, thickness range is 100nm-300nm; The n-In that described 2nd InGaN battery Si adulterates
bga
1-bthe p-In of N layer and Mg doping
bga
1-bn layer, wherein 0.65≤b≤0.85, doping content is 1 × 10
17-1 × 10
19cm
-3, thickness range is 100nm-300nm; The n-In that described 3rd InGaN battery Si adulterates
cga
1-cthe p-In of N layer and Mg doping
cga
1-cn layer, wherein 0.85≤c≤1, doping content is 1 × 10
17-1 × 10
19cm
-3, thickness range is 100nm-300nm.
4. the preparation method of InGaN solar cell is tied in upside-down mounting three according to claim 1, it is characterized in that: described step (2) in the first tunnel junction comprise Si doping n
+-In
aga
1-athe p of N layer and Mg doping
+-In
aga
1-an layer, wherein 0.45≤a≤0.65, doping content is 1 × 10
19-1 × 10
20cm
-3, thickness range is 10nm-50nm; Described second tunnel junction, comprises the n of Si doping
+-In
bga
1-bthe p of N layer and Mg doping
+-In
bga
1-bn layer, wherein 0.65≤b≤0.85, doping content is 1 × 10
19-1 × 10
20cm
-3, thickness range is 10nm-50nm.
5. the preparation method of InGaN solar cell is tied in upside-down mounting three according to claim 1, it is characterized in that: described step (2) middle cap layers is the p of Mg doping
+-In
cga
1-cn, wherein 0.85≤c≤1, doping content is 1 × 10
19-1 × 10
20cm
-3, thickness range is 10nm-100nm.
6. the preparation method of InGaN solar cell is tied in upside-down mounting three according to claim 1, it is characterized in that: described step (2) in translucent current extending be ito film.
7. the preparation method of InGaN solar cell is tied in upside-down mounting three according to claim 1, it is characterized in that: described step (7) in negative electrode be the Ti/Al/Ti/Au of thickness 10/30/10/200nm from top to bottom, it is the n that adulterates in an InGaN battery Si of Ti evaporation at the middle and upper levels
+-In
aga
1-aunder N layer.
8. the preparation method of InGaN solar cell is tied in upside-down mounting three according to claim 1, it is characterized in that: described step (7) middle positive electrode is the Ni of thickness 30nm and the Au of thickness 80nm from top to bottom.
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| CN101101933A (en) * | 2007-07-13 | 2008-01-09 | 南京大学 | Setup method for indium-gallium-nitride p-n node type multi-node solar battery structure |
| CN101232050A (en) * | 2007-01-24 | 2008-07-30 | 中国科学院半导体研究所 | Unijunction indium gallium nitrogen solar battery structure and method for making the same |
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| CN101232050A (en) * | 2007-01-24 | 2008-07-30 | 中国科学院半导体研究所 | Unijunction indium gallium nitrogen solar battery structure and method for making the same |
| CN101101933A (en) * | 2007-07-13 | 2008-01-09 | 南京大学 | Setup method for indium-gallium-nitride p-n node type multi-node solar battery structure |
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Effective date of registration: 20190528 Address after: 300384 No. 6 Huake No. 7 Road, Binhai New Area, Tianjin Binhai High-tech Industrial Development Zone Co-patentee after: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee after: The 18th Research Institute of China Electronics Technology Group Corporation Co-patentee after: China Electric Power Shenzhen Group Co.,Ltd. Address before: 300381 Li Qi Zhuang Ling Chuang-tzu Road, Nankai District, Nankai District, Tianjin Co-patentee before: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee before: The 18th Research Institute of China Electronics Technology Group Corporation |
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Address after: 300384 No. 6 Huake No. 7 Road, Binhai New Area, Tianjin Binhai High-tech Industrial Development Zone Patentee after: The 18th Research Institute of China Electronics Technology Group Corporation Patentee after: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee after: CETC Blue Sky Technology Co.,Ltd. Address before: 300384 No. 6 Huake No. 7 Road, Binhai New Area, Tianjin Binhai High-tech Industrial Development Zone Patentee before: The 18th Research Institute of China Electronics Technology Group Corporation Patentee before: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee before: CETC Energy Co.,Ltd. Address after: 300384 No. 6 Huake No. 7 Road, Binhai New Area, Tianjin Binhai High-tech Industrial Development Zone Patentee after: The 18th Research Institute of China Electronics Technology Group Corporation Patentee after: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee after: CETC Energy Co.,Ltd. Address before: 300384 No. 6 Huake No. 7 Road, Binhai New Area, Tianjin Binhai High-tech Industrial Development Zone Patentee before: The 18th Research Institute of China Electronics Technology Group Corporation Patentee before: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee before: China Electric Power Shenzhen Group Co.,Ltd. |
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| CP01 | Change in the name or title of a patent holder |