CN102738290B - Heterojunction solar battery and preparation method thereof - Google Patents
Heterojunction solar battery and preparation method thereof Download PDFInfo
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- CN102738290B CN102738290B CN201210203828.8A CN201210203828A CN102738290B CN 102738290 B CN102738290 B CN 102738290B CN 201210203828 A CN201210203828 A CN 201210203828A CN 102738290 B CN102738290 B CN 102738290B
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Abstract
The present invention provides a kind of heterojunction solar battery, including a first film with the first conduction type, and the active area and set gradually on the first film surface has the second thin film of the second conduction type, a contact layer with first conduction type mutually heterogeneous with the first film is also included between described the first film and active area, the first film, the second thin film are mutually heterogeneous with active area respectively, and active area is graded bedding structure.The preparation method that the present invention also provides for a kind of a kind of heterojunction solar battery described above, including step: 1) grow mutually heterogeneous with the first film and with conduction type contact layer at the first film exposed surface；2) there is the active area of grading structure in contact layer exposed surface epitaxial growth；3) at the second thin layer that the growth of active area exposed surface is mutually heterogeneous with active area, and the conduction type of the first film and the second thin film is contrary.
Description
Technical field
The present invention relates to area of solar cell, particularly relate to heterojunction solar battery and preparation method thereof.
Background technology
InxGa1-xN energy gap is adjustable in 0.7eV ~ 3.4eV (corresponding wavelength 354nm ~ 1720nm), is the important potential material realizing full spectrum solar cell future.But, owing to the P type of high In ingredient InGaN adulterates the efficiency restriction of difficulty and single junction cell so that the P-N junction battery based on InGaN Quito knot and relatively high In ingredient is still difficult to.Considering that the In component of InGaN can adjust continuously, the solaode based on its grading structure receives much concern.
Traditional solar cell preparation method based on InGaN active area design philosophy, brief step such as Fig. 1, including: step 100, in substrate 205 surface successively grown buffer layer 204, N-type GaN layer 203, form structure such as Fig. 2 A；Step 101, at the active area 202 of N-type GaN layer 203 superficial growth lattice mismatch, forms structure such as Fig. 2 B；Step 102, subsequently in active area 202 superficial growth top layer P type GaN layer 201, forms structure such as Fig. 2 C；Step 103, makes current extending 206, deposits metal, makes P-type layer electrode 207 and N-type layer electrode 210, forms structure such as Fig. 2 D.As shown in Figure 1, Figure 2 shown in A, Fig. 2 B, Fig. 2 C and Fig. 2 D, according to said method, the material that direct growth is bigger with N-type and P type GaN layer lattice paprmeter difference in the growth course of the active area 202 of InGaN, owing to lattice mismatch is high, when growing thicker active area because the reason of Stress Release there will be substantial amounts of misfit dislocation, shown in dislocation 208 in Fig. 2 C, thus reducing the crystalline quality of material and then affecting the performance of solar cell.Simultaneously as the material between active area with N-type and P type GaN layer differs relatively big, therefore the potential barrier of contact is higher, and such as tradition mismatch system solar cell band structure sketch, i.e. Fig. 5 A, this is unfavorable for transporting of carrier, can reduce the efficiency of solar cell.
Summary of the invention
The technical problem to be solved is to provide heterojunction solar battery and preparation method thereof.
In order to solve the problems referred to above, the invention provides a kind of heterojunction solar battery, including a first film with the first conduction type, and the active area and set gradually on the first film surface has the second thin film of the second conduction type, a contact layer with first conduction type mutually heterogeneous with the first film is also included between described the first film and active area, the first film, the second thin film are mutually heterogeneous with active area respectively, and active area is graded bedding structure.
Described heterojunction solar battery, farther includes a substrate and a current extending, and described the first film is arranged on substrate surface, and described current extending is arranged on the second film surface.
The material of active area is InxGa1-xN, x range for 0 to 0.2, and in active area x according to away from substrate direction from 0.2 gradual change to 0.
The material of described contact layer is InGaN or InGaN.
The material of described the first film and the second thin film is GaN.
Described heterojunction solar battery, farther includes a cushion, is placed between substrate and the first film.
In order to solve the problems referred to above, the preparation method that present invention also offers a kind of a kind of heterojunction solar battery described above, including step:
1) mutually heterogeneous with the first film and with conduction type contact layer is grown at the first film exposed surface；
2) there is the active area of grading structure in contact layer exposed surface epitaxial growth；
3) at the second thin layer that the growth of active area exposed surface is mutually heterogeneous with active area, and the conduction type of the first film and the second thin film is contrary.
Farther include step before described step 1): provide a substrate, grow the first film at substrate surface；Step is farther included: grow current extending at the second thin film exposed surface after described step 3).
Described step 2) in the growth of active area all adopt composition change growth or component mutation growth.
Described substrate surface grow the first film step, farther include step: grow a cushion at substrate surface, after buffer-layer surface grow the first film.
The present invention provides heterojunction solar battery and preparation method thereof, and advantage is in that:
The solar cell device preparation method of sapphire substrate surface InGaN/GaN hetero-junctions is made that innovation by the present invention, can obtain the active area of Rational Thickness within the scope of critical thickness, it is to avoid the Carrier recombination loss that the fault in material that lattice mismatch produces is brought；Adopt N-type InGaN contact layer, reduce itself and InxGa1-xThe barrier height of N active area, improves the transport efficiency of carrier；Broader solar spectrum can also be covered simultaneously, improve photoelectric properties and the efficiency of solar cell.
Accompanying drawing explanation
Fig. 1 is method flow diagram prepared by traditional heterogeneous mismatch system solar cell；
Fig. 2 A to 2D is processing step flow chart prepared by traditional heterogeneous mismatch system solar cell device；
Fig. 3 is the method flow diagram of heterojunction solar battery preparation method the second specific embodiment provided by the invention；
Fig. 4 A to 4E is the processing step flow chart that heterojunction solar battery provided by the invention prepares the second specific embodiment；
Fig. 5 A is tradition mismatch system solar cell band structure sketch；
Fig. 5 B is the band structure sketch of heterojunction solar battery provided by the invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, the detailed description of the invention of heterojunction solar battery provided by the invention and preparation method thereof is elaborated.
First specific embodiment
This specific embodiment provides a kind of heterojunction solar battery, structure is as shown in Figure 4 E, including a first film 403 with the first conduction type, and the active area 402 and set gradually on the first film 403 surface has the second thin film 401 of the second conduction type, a contact layer 408 with first conduction type mutually heterogeneous with the first film 403 is also included between described the first film 403 and active area 402, the first film the 403, second thin film 401 is mutually heterogeneous with active area 402 respectively, and active area 402 is graded bedding structure.Contact layer 408 and have the active area 402 of graded bedding, reduces the barrier height between the first film 403 and active area 402 and between the second thin film 401 and active area 402, compared with conventional solar cell, improves the transport efficiency of carrier.
Above-mentioned first conduction type is N-type or P type, and the conduction type of described second conduction type and the first conduction type is contrary.
Described heterojunction solar battery, farther includes substrate 405 and a current extending 406, and described the first film 403 is arranged on substrate 405 surface, and described current extending 406 is arranged on the second thin film 401 surface.
The material of active area 402 is InxGa1-xN, x range for 0 to 0.2, and in active area 402 x according to away from substrate 405 direction from 0.2 gradual change to 0.
The material of described contact layer 408 is InGaN or GaN.
The material of described the first film 403 and the second thin film 401 is GaN.
Described heterojunction solar battery, farther includes a cushion 404, is placed between substrate 405 and the first film 403.
In this specific embodiment, active area 402 adopts graded bedding structure, lattice mismatch can be reduced, avoid the generation of misfit dislocation, with the carrier coincidence loss avoiding the fault in material that lattice mismatch produces to bring, thus being effectively improved device performance, and broader solar spectrum can be covered, improve photoelectric properties and the conversion efficiency of battery.
As optional embodiment, substrate 405 is Sapphire Substrate, silicon substrate and other similar substrate.
As optional embodiment, the first conduction type is N-type or P type.
Described in this specific embodiment, mutually heterogeneous broadband, the forbidden band difference referring to bi-material heterogeneous mutually or lattice paprmeter are different.
As optional embodiment, the material of described active area 402 can also be AlxGa1-xThe ternary material of the GaN systems such as N, wherein x is less than or equal to 1 and be more than or equal to 0.
As optional embodiment, described cushion 404 is AlN or GaN.
As optional embodiment, described current extending 406 is indium tin metal oxide (Indiumtinoxides, ITO).
Second specific embodiment
Fig. 3 show the method flow diagram of described heterojunction solar battery preparation method the second specific embodiment.
Fig. 4 A to 4E show described heterojunction solar battery and prepares the processing step flow chart of the second specific embodiment.
The preparation method that this specific embodiment provides a kind of a kind of heterojunction solar battery as described in the first specific embodiment, including step:
Step 300, grows mutually heterogeneous with the first film and with conduction type contact layer at the first film exposed surface；
Step 301, has the active area of grading structure in contact layer exposed surface epitaxial growth；
Step 302, at the second thin layer that the growth of active area exposed surface is mutually heterogeneous with active area, and the conduction type of the first film and the second thin film is contrary.
As optional embodiment, farther include step before described step 300: provide a substrate 405, at substrate 405 superficial growth the first film 403；Step is farther included: grow current extending 406 at the second thin film 401 exposed surface after described step 303.
As optional embodiment, the growth of the active area 402 with grading structure in described step 301 all adopts composition change growth or component mutation growth.
As optional embodiment, the described step growing the first film 403 at substrate surface 405, farther include step: at substrate 405 superficial growth one cushion 404, after at cushion 404 superficial growth the first film 403.
As optional embodiment, after the second thin film 401 exposed surface grows current extending 406, also include growth N pole contact electrode 407 and contact the step of electrode 410 with P pole.
Next one embodiment of the present of invention is provided.
Fig. 5 A is tradition mismatch system solar cell band structure sketch.
Fig. 5 B show the band structure sketch of described heterojunction solar battery.
The present embodiment provides the preparation method based on graded bedding active area solar cell device, prepares the P-I-N double heterojunction solar battery structure of GaN/InGaN/GaN, wherein eigen I n for sapphire substrate surface0.2Ga0.8N absorbed layer is equivalent to the active area 402 of solar cell, and as shown in Fig. 4 A to Fig. 4 E, processing technology includes following key step:
Step one: with reference to Fig. 4 A, at the first film 403 on Sapphire Substrate 405 surface successively epitaxial growth buffer 404 and N-type GaN layer, this cushion 404 is used for optimizing the first film 403 mass；
MBE is adopted to be grown to example with the active area 402 of InGaN layer, first it is carried out drying up to sample, Sapphire Substrate 405 is put in the preparation room of MBE system, make Sapphire Substrate 405 be warming up to 900 DEG C and to 920 DEG C and remain stable for, remove the steam of residual in Sapphire Substrate 405.Then by the growth room of incoming for Sapphire Substrate 405 MBE system, Sapphire Substrate 405 temperature maintains 720 DEG C, and passes into nitrogen Sapphire Substrate 405 is nitrogenized, and continues 20min.Adopting high growth temperature AlN layer as the cushion 404 of the first film 403 subsequently, underlayer temperature is maintained at about 900 DEG C, and the temperature of Al source stove is 1110 DEG C, grows the cushion 404 of AlN thick for about 80nm.
Carry out the first film 403 of N-type GaN layer when growing, the temperature of Sapphire Substrate 405 is maintained 720 DEG C, the source oven temperature degree of adulterant Si is 1280 DEG C, the BEP(beamequilibriumpressure in Ga source, equivalent beam flow point pressure) it is maintained at 3.7E-7torr, III/V race element flow-rate ratio is about 2.6:1, and Chamber vacuum pressure is 3.05E-5torr, the first film 403 of the N-type GaN layer of about epitaxial growth 400nm.
Above-mentioned BEP is used for determining the flow in source, for instance namely the BEP in Ga source is used for measuring the flow in Ga source.
In the present embodiment, 3.7E-7torr represents 3.7 × 10-7Torr, in literary composition, other are similar to above-mentioned expression.
Step 2: with reference to Fig. 4 B, adopts MBE to grow N-type InGaN contact layer on the first film 403 of N-type GaN layer；
Sapphire Substrate 405 temperature is down to 590 DEG C, In source oven temperature degree is maintained at 805 DEG C, now In source BEP is about 1.7E-7torr, in growth course, Ga source oven temperature degree is 851 DEG C, BEP is maintained at 2.6E-8torr, the source oven temperature degree of adulterant Si is 1280 DEG C, and Chamber vacuum pressure is maintained at 1.3E-5torr, and growth 30min thickness is about the contact layer 408 of the N-type InGaN of 50nm.
Step 3: with reference to Fig. 4 C, adopts MBE to carry out continuously or the growth of the content gradually variational active area 402 of step on contact layer 408 surface；
Here (namely not growing stopping to occur) is grown for composition gradual change, the initial temperature of Sapphire Substrate 405 is 590 DEG C, the initial temperature of In component source stove is 805 DEG C, Sapphire Substrate 405 temperature rises with 0.4 DEG C/min, In source oven temperature degree declines with 0.15 DEG C/min, after growth 100min, Sapphire Substrate 405 temperature is upgraded to 630 DEG C, In source oven temperature degree is down to 790 DEG C, in growth course, Ga source oven temperature degree remains unchanged, temperature is 851 DEG C, and Chamber vacuum pressure is maintained at 1.3E-5torr, and growth thickness is about 160nm.So just can grow In component x fades to the In of 0 from 0.2xGa1-xThe active area 402 of N.
Step 4: with reference to Fig. 4 D, at InxGa1-xSecond thin film 401 of the active area 402 surface epitaxial growth P type GaN layer of N.
Sapphire Substrate 405 temperature rises to 685 DEG C, the source oven temperature degree of P type Mg adulterant is 270 DEG C, and the BEP in Ga source is maintained at 8.3E-8torr, III/V race element flow-rate ratio and is about 1.05:1, Chamber vacuum pressure is 1.3E-5torr, and the P type GaN layer of about epitaxial growth 200nm is as the second thin film 401.
Step 5: with reference to Fig. 4 E, makes current extending 406, Deposit contact electrode 407,410.
Second thin film 401 evaporates ITO indium tin metal oxide (Indiumtinoxides, ITO) of 180nm.Carry out a photoetching, make mask with photoresist and adopt inductively coupled plasma (Inductivecoupleplasmas, ICP) etch from current extending 406 toward Sapphire Substrate 405 direction, until manifesting the first film 403, form ledge structure, remove photoresist, annealing, the second thin film 401 making ITO and P type GaN forms Ohmic contact, thus forming current extending 406.Carry out secondary photoetching, evaporate Ti/Al/Ti/Au, utilize method the first film 403 surface below current extending 406 surface and step peeled off to make P pole contact electrode 410 respectively and contact electrode 407 with N pole, as shown in Figure 4 E.
The method of above-mentioned stripping can adopt organic solvent-acetone to carry out the stripping of photoresist.
With reference to energy band diagram 5B, the present embodiment adopts contact layer 408, there is the structure of the active area 402 of grading structure, be beneficial to transporting of carrier, the efficiency of solaode can be improved.
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention; can also making some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (8)
1. a heterojunction solar battery, including a first film with the first conduction type, and the active area and set gradually on the first film surface has the second thin film of the second conduction type, it is characterized in that, a contact layer with first conduction type mutually heterogeneous with the first film is also included between described the first film and active area, the first film, the second thin film are mutually heterogeneous with active area respectively, active area is graded bedding structure, the material of described contact layer is N-type InGaN, and the material of described active area is InxGa1-xN, x range for 0 to 0.2, and in active area x according to away from substrate direction from 0.2 gradual change to 0.
2. heterojunction solar battery according to claim 1, it is characterised in that farther include a substrate and a current extending, described the first film is arranged on substrate surface, and described current extending is arranged on the second film surface.
3. heterojunction solar battery according to claim 1, it is characterised in that the material of described the first film and the second thin film is GaN.
4. heterojunction solar battery according to claim 2, it is characterised in that farther include a cushion, be placed between substrate and the first film.
5. the preparation method of the heterojunction solar battery described in a claim 1, it is characterised in that include step: 1) grow mutually heterogeneous with the first film and with conduction type contact layer at the first film exposed surface；2) there is the active area of grading structure in contact layer exposed surface epitaxial growth；3) at the second thin layer that the growth of active area exposed surface is mutually heterogeneous with active area, and the conduction type of the first film and the second thin film is contrary, and the material of described contact layer is N-type InGaN, and the material of described active area is InxGa1-xN, x range for 0 to 0.2, and in active area x according to away from substrate direction from 0.2 gradual change to 0.
6. the preparation method of heterojunction solar battery according to claim 5, it is characterised in that farther include step before described step 1): provide a substrate, grows the first film at substrate surface；Step is farther included: grow current extending at the second thin film exposed surface after described step 3).
7. the preparation method of heterojunction solar battery according to claim 5, it is characterised in that described step 2) in the growth of active area all adopt composition change growth or component mutation growth.
8. the preparation method of heterojunction solar battery according to claim 6, it is characterised in that described substrate surface grow the first film step, farther include step: grow a cushion at substrate surface, after buffer-layer surface grow the first film.
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| CN101330118A (en) * | 2007-06-22 | 2008-12-24 | 晶能光电（江西）有限公司 | Method for producing p type semiconductor structure |
| CN101911312A (en) * | 2008-01-07 | 2010-12-08 | 罗斯特里特实验室能源公司 | Has the group iii-nitride solar cell that gradual change is formed |
| 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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| KR101034055B1 (en) * | 2003-07-18 | 2011-05-12 | 엘지이노텍 주식회사 | Light emitting diode and method for manufacturing light emitting diode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101330118A (en) * | 2007-06-22 | 2008-12-24 | 晶能光电（江西）有限公司 | Method for producing p type semiconductor structure |
| CN101911312A (en) * | 2008-01-07 | 2010-12-08 | 罗斯特里特实验室能源公司 | Has the group iii-nitride solar cell that gradual change is formed |
| 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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