CN102738311B - Preparation method of InGaN/Si double-node solar cell - Google Patents
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- CN102738311B CN102738311B CN201210246406.9A CN201210246406A CN102738311B CN 102738311 B CN102738311 B CN 102738311B CN 201210246406 A CN201210246406 A CN 201210246406A CN 102738311 B CN102738311 B CN 102738311B
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Abstract
The invention relates to a preparation method of an InGaN/Si double-node solar cell, which comprises the following steps of: sequentially growing an AlN nucleating layer, a GaN buffer layer, an n-InxGa1-xN layer and a p-InxGa1-xN layer on an n-Si substrate; and carrying out evaporation plating on positive and negative electrodes. The preparation method has the characteristics that 1, a p-Si layer is prepared between the n-Si substrate and the AlN nucleating layer; 2, a semitransparent current expansion layer on the p-InxGa1-xN layer; and 3, the negative electrode is prepared at the reverse side of the n-Si substrate. According to the invention, the p-Si layer is arranged between the n-Si substrate and the AlN nucleating layer, so the Si bottom cell is formed by the p-Si layer and the n-Si substrate, the cell is easy to prepare and the total conversion efficiency of the cell is high; the semitransparent current expansion layer is subjected to evaporation plating, so that the cell has strong anti-radiation capacity and has long service life; and the negative electrode is formed on the lower surface of the n-Si substrate by evaporation plating, so that the process is simplified, the cost is reduced and the InGaN/Si double-node solar cell can also be used as a reflector, and thus, the total conversion efficiency of the cell is further improved.
Description
Technical field
The invention belongs to technical field of solar cells, particularly relate to a kind of preparation method of InGaN/Si double-junction solar battery.
Background technology
The current known energy is all non-renewable, after exploitation for many years, the reserves of these energy are all reducing day by day, and can cause serious environmental problem 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 of finding diligently solar energy high conversion efficiency.In recent years, with GaN and InGaN, the third generation semi-conducting material that AlGaN is representative---III group-III nitride is the focus that people study, and 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 report 1.89eV but 0.7eV, this just means by regulating In component in InGaN material, can make its energy gap adjustable continuously to 0.7eV (InN) from 3.4eV (GaN), 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 caused people's close attention.
Sapphire and silicon carbide substrates are that current growing InGaN uses maximum materials, use the preparation technology of Sapphire Substrate very ripe, but its hardness is high, conduction and poor heat conductivity, have limited the performance of InGaN device; Silicon carbide substrates is compared Sapphire Substrate and is had better performance, but it is expensive, has limited its application; And silicon substrate not only hardness and price low, and there is easy cleavage, be easy to get large-area high-quality commercialization substrate and silicon-based devices be easy to integrated, band gap is the advantages such as 1.12eV, be considered to be hopeful most to replace a kind of ideal material of above two kinds of substrate growing InGaNs, but there is the problem of lattice mismatch and thermal expansion mismatch in silicon substrate.
Find through retrieval, how people adopts Si substrate growing InGaN material to prepare solar cell if beginning one's study, and overcome the problem of lattice mismatch and thermal expansion mismatch.As: application number is 200810240351.4, name is called the patent of invention of " p-i-n type InGaN quantum dot solar battery structure and preparation method thereof ", structure comprises: a substrate, is followed successively by low temperature gallium nitride nucleating layer, non-doped gallium nitride resilient coating intentionally, N-shaped doping In on it
xga
1-xn layer, non-doping i layer In
yga
1-yn quantum-dot structure and p-type doping In
xga
l-xn layer; Application number is 201110300096.X, name is called the patent of invention of " the p-i-n type InGaN solar cell that contains superlattice structure ", structure comprises: a substrate, on it, be followed successively by high temperature AlN nucleating layer, non-doped gallium nitride resilient coating, N-shaped Doped GaN layer, InGaN/GaN superlattice and p-type Doped GaN layer intentionally, and there is Ni/Au electrode on p-type GaN layer surface, there is Al/Au electrode on N-shaped GaN layer surface.
It is solar cell that the above-mentioned patent retrieving all adopts Si to prepare InGaN as substrate, has solved the problem of lattice mismatch and thermal expansion mismatch, but owing to having increased the complexity of epitaxy technique, has reduced the total conversion efficiency of battery, has improved production cost.
Summary of the invention
The present invention solves the problem that prior art exists, and provides that one is easy to preparation, total conversion efficiency is high, capability of resistance to radiation is strong, long service life, and the preparation method of the low a kind of InGaN/Si double-junction solar battery of production cost.
The preparation method of InGaN/Si double-junction solar battery of the present invention adopts following technical scheme:
A preparation method for InGaN/Si double-junction solar battery, preparation process comprises that the n-Si layer of selecting after cleaning is as n-Si substrate; Adopting metal organic chemical vapor deposition technology is MOCVD growing AIN nucleating layer on n-Si substrate; Growing GaN resilient coating on AlN nucleating layer; N-In grows on GaN resilient coating
xga
1-xn layer; At n-In
xga
1-xp-In grows on N layer
xga
1-xn layer, and evaporation positive and negative electrode, be characterized in: further comprising the steps of in preparation process:
1. p-Si layer processed between described n-Si substrate and AlN nucleating layer
Above described n-Si substrate, before growing AIN nucleating layer, pass into the TMAl of flow 20-40mL/min and the NH of flow 2-5L/min
3in the time of 500-700 DEG C, Al atom starts to be diffused into alternative Si atom in n-Si layer, form surface highly doped, then be warming up to 1000-1100 DEG C, Al atom further spreads, and with the p-Si layer of n-Si substrate formation junction depth 0.01-0.5um, grows the described AlN nucleating layer of thickness 50-100nm above p-Si layer; The p-Si layer forming between AlN nucleating layer and n-Si layer and n-Si layer have formed battery at the bottom of Si;
2. at described p-In
xga
1-xthe translucent current extending of evaporation on N layer
P-In will grow
xga
1-xsubstrate after N layer and ITO material are placed in electron beam evaporation equipment, and vacuum degree is set to 10
-4below Pa, pass into the oxygen that flow is 2-5sccm simultaneously, when temperature is 150-300 DEG C, evaporation 1-3 hour, p-In
xga
1-xon N layer, form the ITO film that 150-350nm is thick; Take out the material after evaporation, then put into annealing furnace, the N of 350-500 DEG C
2under environment, annealing 10-20 minute, cools to normal temperature with the furnace, p-In
xga
1-xiTO film on N layer is translucent current extending; On translucent current extending, making the degree of depth by lithography is the positive electrode region of 50-100nm, the remainder formation covered by photoresist protection zone of translucent current extending; At described positive electrode region evaporation positive electrode;
3. at n-Si substrate back evaporation negative electrode
, be placed in electron beam evaporation equipment by the back side of n-Si substrate upward, on the back side of n-Si substrate, evaporation Ti/Pd/Ag negative electrode, completes the making of InGaN/Si double-junction solar battery.
The preparation method of InGaN/Si double-junction solar battery of the present invention can also adopt following technical measures:
The described positive electricity Ni/Au electrode that very 20nm/60nm is thick.
The described negative electricity Ti/Pd/Ag electrode that very 15nm/15nm/400nm is thick.
The advantage that the present invention has and good effect:
1, the present invention adopts n-Si substrate, the diffusion of Al atom during by growing AIN nucleating layer has formed p-Si layer between n-Si substrate and AlN nucleating layer, and p-Si layer and n-Si substrate have formed battery at the bottom of Si, not only be easy to preparation, and it is high to be prepared into the total conversion efficiency of battery;
2, the present invention, by the translucent current extending of evaporation, has strengthened the collection of positive electrode to charge carrier, has improved the capability of resistance to radiation of battery, has extended the useful life of battery;
3, the present invention, due to direct evaporation negative electrode below n-Si substrate, has simplified technique, has reduced cost, and the negative electrode of evaporation can also use as speculum like this, further improve the total conversion efficiency of battery.
Brief description of the drawings
Fig. 1 is InGaN/Si double-junction solar battery structural representation prepared by the present invention;
Fig. 2 is positive electrode region and the protection zone making by lithography on translucent current extending in Fig. 1.
In figure, 1-n-Si substrate, 2-p-Si layer, 3-AlN nucleating layer, 4-GaN resilient coating, 5-n-In
xga
1-xn layer, 6-p-In
xga
1-xn layer, the translucent current extending of 7-, 8-positive electrode, 9-negative electrode, 10-positive electrode region, 11-protection zone.
Embodiment
For further disclosing summary of the invention of the present invention, Characteristic, be also elaborated by reference to the accompanying drawings as follows especially exemplified by following instance:
The preparation method of InGaN/Si double-junction solar battery, preparation process comprises that the n-Si selecting after cleaning is as substrate; Adopting metal organic chemical vapor deposition technology is MOCVD growing AIN nucleating layer on n-Si substrate; Growing GaN resilient coating on AlN nucleating layer; N-In grows on GaN resilient coating
xga
1-xn layer; At n-In
xga
1-xp-In grows on N layer
xga
1-xn layer, and evaporation positive and negative electrode.
Innovative point of the present invention is: further comprising the steps of in preparation process:
1. between described n-Si substrate and AlN nucleating layer, form p-Si layer
Above described n-Si substrate, before growing AIN nucleating layer, pass into the TMAl of flow 20-40mL/min and the NH of flow 2-5L/min
3in the time of 500-700 DEG C, Al atom starts to be diffused into alternative Si atom in n-Si layer, form surface highly doped, then be warming up to 1000-1100 DEG C, Al atom further spreads, and with the p-Si layer of n-Si substrate formation junction depth 0.01-0.5um, grows the described AlN nucleating layer of thickness 50-100nm above p-Si layer; The p-Si layer forming between AlN nucleating layer and n-Si layer and n-Si layer have formed battery at the bottom of Si;
2. at described p-In
xga
1-xthe translucent current extending of evaporation on N layer
P-In will grow
xga
1-xsubstrate after N layer and ITO material are placed in electron beam evaporation equipment, and vacuum degree is set to 10
-4below Pa, pass into the oxygen that flow is 2-5sccm simultaneously, when temperature is 150-300 DEG C, evaporation 1-3 hour, p-In
xga
1-xon N layer, form the ITO film that 150-350nm is thick; Take out the material after evaporation, then put into annealing furnace, the N of 350-500 DEG C
2under environment, annealing 10-20 minute, cools to normal temperature with the furnace, p-In
xga
1-xiTO film on N layer is translucent current extending; On translucent current extending, making the degree of depth by lithography is the positive electrode region of 50-100nm, the remainder formation covered by photoresist protection zone of translucent current extending; At described positive electrode region evaporation positive electrode;
3. at n-Si substrate back evaporation negative electrode
, be placed in electron beam evaporation equipment by the back side of n-Si substrate upward, on the back side of n-Si substrate, evaporation Ti/Pd/Ag negative electrode, completes the making of InGaN/Si double-junction solar battery.
Embodiment: with reference to accompanying drawing 1-Fig. 2:
Step 1, select n-Si after ultrasonic cleaning as substrate;
Step 2, employing metal organic chemical vapor deposition technology (MOCVD), be placed in reative cell by n-Si substrate 1, passes into TMAl flow 30mL/min and NH
3flow 3L/min, 600 DEG C of conditions, Al atom starts to be diffused into alternative Si atom in n-Si layer, form surface highly doped, be then warming up to 1000 DEG C, Al atom further spreads, p-Si layer 2 with n-Si substrate formation junction depth 0.1um, grows the AlN nucleating layer 3 that 60nm is thick above p-Si layer; Wherein p-Si layer and n-Si layer have formed battery at the bottom of Si, are not only easy to preparation, and the total conversion efficiency that is prepared into battery can reach more than 30%;
Step 3, employing metal organic chemical vapor deposition technology growing GaN resilient coating 4 on AlN nucleating layer, growth temperature is 1000 DEG C, and thickness is 1 μ m, and this layer can reduce the defect concentration of epitaxial loayer, thereby improves crystal mass;
The n-In of step 4, the Si that grows on GaN resilient coating doping
xga
1-xn layer 5, growth temperature is 1000 DEG C, wherein x is 0.46, doping content 5 × 10
18, thickness 200nm, has ensured the absorption of light and the diffusion in hole;
Step 5, at n-In
xga
1-xthe p-In of the Mg that grows on N layer doping
xga
1-xn layer 6, growth temperature is 1000 DEG C, wherein x is 0.46, doping content 5 × 10
18, thickness range is 100nm, and enough electric charges can be provided, and suitable top metal contact conditions;
Step 6, at p-In
xga
1-xthe translucent current extending 7 of evaporation on N layer:
Substrate and ITO material after step 5 is grown are placed in electron beam evaporation equipment, and its vacuum degree is 10
-4below Pa, pass into the oxygen that flow is 3.5sccm, temperature is 200 DEG C simultaneously, evaporation 2 hours, p-In
xga
1-xon N layer, form the ITO film that 200nm is thick; Take out the material after evaporation, then put into annealing furnace, the N of 450 DEG C
2under environment, anneal 15 minutes, cool to normal temperature with the furnace, p-In
xga
1-xiTO film on N layer is translucent current extending, has strengthened the collection of positive electrode to charge carrier, has improved the capability of resistance to radiation of battery, has extended the useful life of battery;
Step 7, the translucent current extending of photoetching
Adopt mask aligner, on translucent current extending, make by lithography as shown in Figure 2, the positive electrode region 10 that the degree of depth is 80nm, the remainder encirclement covered by photoresist of translucent current extending forms protection zone 11;
Step 8, evaporation positive electrode 8:
Material after step 7 photoetching and Au, Ni are placed in to electron beam evaporation equipment, and its vacuum degree is 10
-4when Pa is following, start evaporation, positive electrode region evaporation goes out the Ni of a layer thickness 20nm, and on Ni, evaporation goes out a layer thickness 60nm Au, and in whole evaporate process, temperature is that 100 DEG C, evaporation time are 2 hours; At the N of 550 DEG C
2under environment, anneal 5 minutes, naturally cool to after normal temperature with stove, the positive electrode region of translucent current extending is that evaporation goes out from bottom to top to become one, Ni/Au positive electrode that thickness is 20nm/60nm;
Step 9, evaporation negative electrode 9:
By the n-Si substrate back of material after step 8 evaporation positive electrode upward, be placed in electron beam evaporation equipment, and Ti, Pd and Ag are together placed in to electron beam evaporation equipment, its vacuum degree is 10
-4when Pa is following, start evaporation, in the bottom surface of n-Si substrate successively evaporation go out thickness 15nm Ti, 15nm (Ag of Pd and 400nm, in whole evaporate process, temperature is 100 DEG C, evaporation 2 hours; The N of 750 DEG C
2under environment, anneal 5 minutes, naturally cool to after normal temperature with stove, the back side evaporation of n-Si substrate goes out that battery location shown in Fig. 1 becomes one from top to bottom, the Ti/Pd/Ag negative electrode of thickness 15nm/15nm/400nm, completes the preparation method's of InGaN/Si double-junction solar battery of the present invention making.The preparation process of this negative pole has been simplified technique, has reduced cost, and can use as speculum, has further improved the total conversion efficiency of battery.
Although by reference to the accompanying drawings the preferred embodiments of the present invention are described above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing from the scope situation that aim of the present invention and claim protect, can also make a lot of forms.Within these all belong to protection scope of the present invention.
Claims (3)
1. a preparation method for InGaN/Si double-junction solar battery, preparation process comprises that the n-Si layer of selecting after cleaning is as n-Si substrate; Adopting metal organic chemical vapor deposition technology is MOCVD growing AIN nucleating layer on n-Si substrate; Growing GaN resilient coating on AlN nucleating layer; N-In grows on GaN resilient coating
xga
1-xn layer; At n-In
xga
1-xp-In grows on N layer
xga
1-xn layer, and evaporation positive and negative electrode, is characterized in that: further comprising the steps of in preparation process:
1. between described n-Si substrate and AlN nucleating layer, form p-Si layer
Above described n-Si substrate, before growing AIN nucleating layer, pass into the TMAl of flow 20-40mL/min and the NH of flow 2-5L/min
3in the time of 500-700 DEG C, Al atom starts to be diffused into alternative Si atom in n-Si layer, form surface highly doped, then be warming up to 1000-1100 DEG C, Al atom further spreads, and with the p-Si layer of n-Si substrate formation junction depth 0.01-0.5um, grows the described AlN nucleating layer of thickness 50-100nm above p-Si layer; The p-Si layer forming between AlN nucleating layer and n-Si layer and n-Si layer have formed battery at the bottom of Si;
2. at described p-In
xga
1-xthe translucent current extending of evaporation on N layer
P-In will grow
xga
1-xsubstrate after N layer and ITO material are placed in electron beam evaporation equipment, and vacuum degree is set to 10
-4below Pa, pass into the oxygen that flow is 2-5sccm simultaneously, when temperature is 150-300 DEG C, evaporation 1-3 hour, p-In
xga
1-xon N layer, form the ITO film that 150-350nm is thick; Take out the material after evaporation, then put into annealing furnace, the N of 350-500 DEG C
2under environment, annealing 10-20 minute, cools to normal temperature with the furnace, p-In
xga
1-xiTO film on N layer is translucent current extending; On translucent current extending, making the degree of depth by lithography is the positive electrode region of 50-100nm, the remainder formation covered by photoresist protection zone of translucent current extending; At described positive electrode region evaporation positive electrode;
3. at n-Si substrate back evaporation negative electrode
, be placed in electron beam evaporation equipment by the back side of n-Si substrate upward, on the back side of n-Si substrate, evaporation Ti/Pd/Ag negative electrode, completes the making of InGaN/Si double-junction solar battery.
2. the preparation method of InGaN/Si double-junction solar battery according to claim 1, is characterized in that: the described positive electricity Ni/Au electrode that very 20nm/60nm is thick.
3. the preparation method of InGaN/Si double-junction solar battery according to claim 1, is characterized in that: the described negative electricity Ti/Pd/Ag electrode that very 15nm/15nm/400nm is thick.
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| CN103325878B (en) * | 2013-05-31 | 2015-12-23 | 西安电子科技大学 | A kind of p-i-n type InGaN/p-n type Si binode stacked solar cell, cascade solar cell and preparation method thereof |
| CN104347753A (en) * | 2013-08-01 | 2015-02-11 | 中国电子科技集团公司第十八研究所 | Preparation method of InGaN/Si three-junction solar cell |
| CN110137294A (en) * | 2019-05-20 | 2019-08-16 | 深圳市科创数字显示技术有限公司 | A kind of nitride multijunction solar cell and preparation method thereof |
| CN110265502A (en) * | 2019-06-13 | 2019-09-20 | 深圳市科创数字显示技术有限公司 | A kind of silicon substrate indium nitride solar battery and preparation method thereof |
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| CN101866967A (en) * | 2010-04-30 | 2010-10-20 | 华中科技大学 | Solar cell |
| CN102290478A (en) * | 2011-09-05 | 2011-12-21 | 中国电子科技集团公司第十八研究所 | p-i-n-type unijunction InGaN solar cell |
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| CN102403377A (en) * | 2011-11-01 | 2012-04-04 | 宁波市鑫友光伏有限公司 | N-type substrate silicon solar cell and production method thereof |
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| KR100581840B1 (en) * | 2004-04-21 | 2006-05-22 | 한국전기연구원 | Light sensitized and P-N junction complexed solar cell and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101866967A (en) * | 2010-04-30 | 2010-10-20 | 华中科技大学 | Solar cell |
| CN102290478A (en) * | 2011-09-05 | 2011-12-21 | 中国电子科技集团公司第十八研究所 | p-i-n-type unijunction InGaN solar cell |
| CN102339891A (en) * | 2011-09-29 | 2012-02-01 | 西安电子科技大学 | InGaN solar cell with p-i-n sandwich structure |
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Effective date of registration: 20190529 Address after: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Co-patentee after: The 18th Research Institute of China Electronics Technology Group Corporation Patentee after: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Co-patentee after: China Electric Power Shenzhen Group Co.,Ltd. Address before: 300384 No. 15, Sidao, Haitai Development, Huayuan Industrial Park, Xiqing District, Tianjin Co-patentee before: The 18th Research Institute of China Electronics Technology Group Corporation Patentee before: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. |
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Address after: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Patentee after: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee after: The 18th Research Institute of China Electronics Technology Group Corporation Patentee after: CETC Blue Sky Technology Co.,Ltd. Address before: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Patentee before: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee before: The 18th Research Institute of China Electronics Technology Group Corporation Patentee before: CETC Energy Co.,Ltd. Address after: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Patentee after: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee after: The 18th Research Institute of China Electronics Technology Group Corporation Patentee after: CETC Energy Co.,Ltd. Address before: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Patentee before: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee before: The 18th Research Institute of China Electronics Technology Group Corporation Patentee before: China Electric Power Shenzhen Group Co.,Ltd. |