CN115020547A - Forming process of laser photovoltaic device - Google Patents
Forming process of laser photovoltaic device Download PDFInfo
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- 239000002184 metal Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 238000005530 etching Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 239000004065 semiconductor Substances 0.000 claims abstract description 4
- 238000002955 isolation Methods 0.000 claims description 30
- 238000001259 photo etching Methods 0.000 claims description 18
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 16
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- 238000005260 corrosion Methods 0.000 claims description 13
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 12
- 238000000407 epitaxy Methods 0.000 claims description 11
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
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- 238000011049 filling Methods 0.000 claims description 6
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 6
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- 230000005641 tunneling Effects 0.000 claims description 6
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- 229910052794 bromium Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 3
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Abstract
The invention discloses a forming process of a laser photovoltaic device, which belongs to the technical field of photovoltaic cells and comprises the following steps: epitaxially preparing an active layer of the reverse III-V semiconductor laser battery; transferring the active layer of the battery to an insulating substrate by adopting a graphic metal bonding process; manufacturing an upper electrode and a bridging electrode of the battery; manufacturing a cell surface antireflection structure; and scribing and dividing the internal cascade laser photovoltaic devices. The invention introduces the graphic metal bonding technology into the preparation process of the laser photovoltaic device, and only carries out one-time etching process in the whole process, thereby reducing the loss of the effective area of the battery caused by side etching in the etching. The photoelectric conversion efficiency of the cell can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of photovoltaic cells, and particularly relates to a forming process of a laser photovoltaic device.
Background
The current space on-orbit activities are increasing, including rendezvous and docking, astronauts taking out of capsule, on-orbit maintenance and service and the like. In more and more space non-stationary activities, there is a need to solve the problem of energy supply to flexible track equipment. Laser wireless energy transfer is an effective means for solving the problem of on-orbit energy supply. In the laser wireless energy transmission system, laser can convert light energy into electric energy through a photovoltaic cell to be used by related equipment, so that the laser receiving module is one of the most important components of the laser wireless energy transmission system.
The voltage of the unijunction laser battery is small, and the energy density of incident laser is far greater than that of sunlight, so that the working current of the unijunction laser battery is large, and the excessive current causes higher energy loss in a circuit, thereby reducing the photoelectric conversion efficiency of the laser battery. In the traditional method, laser batteries are connected in series to form an assembly, so that the voltage is increased, and the output current is reduced. When the batteries are spliced into the assembly, the effective light receiving area of the battery assembly is reduced by the splicing gap, and higher series resistance is introduced into electrode welding spots among the batteries.
Therefore, how to increase the effective power generation area of the laser battery, reduce the series resistance introduced by the electrode welding spot, and further improve the photoelectric conversion efficiency of the laser battery becomes a technical problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to provide a forming process of a laser photovoltaic device, which integrates laser photovoltaic battery units into the same substrate in a heterogeneous manner, can further improve the effective power generation area of the laser photovoltaic, reduces series resistance introduced by electrode welding spots, and simplifies the etching process of an isolation groove.
The invention aims to provide a forming process of a laser photovoltaic device, which comprises the following steps:
step S01, epitaxially preparing an active layer of the reverse III-V semiconductor laser battery on the first substrate;
step S02, preparing patterned metal layers with the same size on the epitaxial surface of the first substrate and the second substrate by adopting a photoetching process, wherein the metal layers comprise alignment marks and are used as bonding metal layers and lower electrodes of batteries;
step S03, aligning the epitaxial surface of the first substrate with the patterned metal layer on the second substrate through the alignment mark, and carrying out metal bonding;
step S04, removing the first substrate by adopting a substrate stripping multiplexing technology to finish the transfer of the epitaxial layer to the second substrate;
step S05, photoetching an isolation groove pattern according to the patterned lower electrode by adopting a photoetching sleeve process;
step S06, etching the isolation groove, completely etching the epitaxial active layer of the battery, and exposing the lower electrode cutting gap and the lower electrode bridging lead point;
step S07, filling the passivation isolation groove with insulating glue;
step S08, manufacturing an upper electrode on the surface of the battery by adopting a photoetching sleeve process, and manufacturing insulating glue for bridging the electrodes to cross the filling of the isolation grooves to connect the upper electrode and the lower electrode of the sub-battery;
step S09, corroding a cap layer on the surface of the battery, manufacturing an antireflection film on the surface of the battery, and manufacturing a nano array structure on the antireflection film;
and step S10, scribing, and cutting the inner cascade laser photovoltaic device.
As an alternative, in step S01, the reverse GaAs-based laser cell active layer is prepared by MOCVD epitaxy: the specific process comprises the following steps:
s101, adopting a GaAs substrate as a first substrate;
s102, epitaxially growing a GaInAs buffer layer;
s103, epitaxially growing an AlAs sacrificial layer;
s104, epitaxially growing a GaAs cap layer:
s105, growing a first Ga (in) As sub-battery in a reverse epitaxial mode;
s106, epitaxially growing a tunneling junction;
s107, growing a second Ga (in) As sub-battery in a reverse epitaxial mode;
and S108, epitaxially growing a GaAs cap layer.
As another alternative, in step S01, the reverse InP-based laser cell active layer is epitaxially prepared using MOCVD: the specific process comprises the following steps:
s001, adopting an InP substrate as a first substrate;
s002, epitaxially growing an InP buffer layer;
s003, epitaxially growing an AlAs sacrificial layer;
s004, epitaxially growing a GaInAs cap layer;
s005, growing a first GaInAsP sub-battery by reverse epitaxy;
s006, epitaxially growing a tunneling junction;
s007, growing a second GaInAsP sub-battery through reverse epitaxy;
and S008, epitaxially growing a GaInAs cap layer.
Further, in step S02, the second substrate is an insulating substrate, and the substrate material is silicon oxide, polyimide, or quartz. And preparing a metal layer Ti/Ag/Au by adopting an evaporation process, wherein the evaporation rate is 5-50 nm/min.
Further, in step S03, the bonding temperature is 200-400 ℃, the bonding pressure is 0.3-0.8 Mpa, and the bonding annealing time is 10-40 min;
further, in step S04, the substrate peeling multiplexing technique is: and corroding the AlAs sacrificial layer by using HF acid, wherein the concentration of the HF acid is 10-25%, the corrosion temperature is 40-60 ℃, and the corrosion time is 5-30 h.
Further, in step S05, in the case that the spacing between the photolithographic isolation trench pattern and the bottom electrode pattern is consistent, the isolation trench of the bottom electrode bridge connection point is added.
Further, in step S06, etching all the cell epitaxial active layer materials in the isolation trench by using a bromine-based etching solution until the lower electrode partition gap and the lower electrode bridge connection point are exposed, wherein the etching rate is 100-800 nm/min.
Further, in step S07, the insulating glue is polyimide glue, and the curing temperature is 100 to 300 ℃.
Further, in step S08, a metal layer Ti/Ag/Au is prepared by an evaporation process, wherein the evaporation rate is 5-50 nm/min.
Further, in step S09, citric acid: hydrogen peroxide: and (3-6) corroding the cap layer with the corrosion rate of 50-200 nm/min.
Further, in step S09, a titanium oxide/silicon oxide antireflection film is prepared by PECVD, with a deposition rate of 5 to 50 nm/min. And (3) adopting a nano-imprinting process to manufacture a nano-array structure.
Further, in step S10, a grinding wheel dicing saw is used for dicing, the particle size of the dicing saw is 3-6 μm, and the rotating speed is 30000-40000 r/min.
The invention has the advantages that:
1. the process adopts a graphic metal bonding technology, integrates the battery units of the laser photovoltaic device on the same substrate in a heterogeneous mode, and is higher in integration level and larger in effective power generation area.
2. In the traditional process, in order to leave a bridging electrode lead point, different III-V semiconductor materials can be removed by adopting different chemical solutions for alternative corrosion in an isolation groove etching process. In the process, the patterned metal bonding layer is used as the lower electrode of the battery, the whole process is only subjected to one-time etching process, and the epitaxial layer is etched to the bottom by adopting bromine-based corrosive liquid, so that the process is simplified, the etching times are reduced, and the loss of the effective area of the battery caused by side etching in the etching process is also reduced.
3. In the process, the upper electrode and the bridging electrode of the battery are integrally prepared in the same process, so that series resistance caused by electrode interconnection welding spots in the traditional process is avoided.
Drawings
FIG. 1 is a schematic flow diagram of a laser photovoltaic device forming process of the present invention
Detailed Description
To further understand the contents, features and effects of the present invention, the following embodiments are illustrated, and the process flow diagram of fig. 1 is described in detail as follows:
a forming process of a GaAs laser photovoltaic device with a 808nm waveband comprises the following steps:
step S01, preparing a reverse GaAs-based laser battery active layer by MOCVD epitaxy, which comprises the following specific steps:
s101, adopting an n-type doped GaAs substrate with a thickness of 200- 17 ~1×10 18 cm -3 ;
S102, epitaxially growing a GaInAs buffer layer with the thickness of 50-100 nm;
s103, epitaxially growing an AlAs sacrificial layer with the thickness of 50-100 nm;
s104, epitaxially growing an n-type GaAs cap layer with the thickness of 100-200 nm and the doping concentration of 1 multiplied by 10 18 ~1×10 19 cm -3 ;
S105, growing a first Ga (in) As sub-battery in a reverse epitaxial mode;
s106, epitaxially growing a tunneling junction;
s107, growing a second Ga (in) As sub-battery in a reverse epitaxial mode;
s108, epitaxially growing a p-type GaAs cap layer with the thickness of 100-200 nm and the doping concentration of 1 multiplied by 10 18 ~1×10 19 cm -3 。
And step S02, preparing a patterned metal layer with the same size on the GaAs epitaxial wafer and the silicon oxide substrate by adopting a photoetching process, wherein the metal layer comprises an alignment mark and is used as a bonding metal layer and a battery lower electrode. Wherein, a vapor deposition process is adopted to prepare a metal layer Ti/Ag/Au, the evaporation rate is 5-50 nm/min, and the total thickness is 3-6 μm;
and step S03, aligning the GaAs epitaxial wafer with the patterned metal layer on the silicon oxide substrate through the alignment mark, and carrying out metal bonding. Wherein the bonding temperature is 200-400 ℃, the bonding pressure is 0.3-0.8 Mpa, and the bonding annealing time is 10-40 min;
and step S04, removing the GaAs substrate by adopting a substrate stripping multiplexing technology, and finishing the transfer of the epitaxial layer to the silicon oxide substrate. Wherein, the AlAs sacrificial layer is corroded by HF acid, the concentration of the HF acid is 10-25%, the corrosion temperature is 40-60 ℃, and the corrosion time is 5-30 h;
and step S05, photoetching a battery isolation groove pattern according to the patterned lower electrode by adopting a photoetching sleeve process. The isolation groove of the lower electrode bridge connection point is added under the condition that the interval between the photoetching isolation groove graph and the lower electrode graph is consistent;
and step S06, etching the isolation groove, completely etching the epitaxial active layer of the cell, and exposing the lower electrode cutting gap and the lower electrode bridging point. Etching all the epitaxial active layer materials of the cells in the isolation groove by adopting bromine-based corrosive liquid, wherein the etching rate is 100-800 nm/min;
s07, filling a passivation isolation groove with insulating glue, wherein the insulating glue is polyimide glue, and the curing temperature is 100-300 ℃;
and step S08, manufacturing an upper electrode on the surface of the battery by adopting a photoetching sleeve process, and manufacturing a bridging electrode to cross the insulating glue filled in the isolation groove to connect the upper electrode and the lower electrode of the sub-battery. Wherein, a vapor deposition process is adopted to prepare a metal layer Ti/Ag/Au, the evaporation rate is 5-50 nm/min, and the total thickness is 3-6 μm;
and S09, corroding the cap layer on the surface of the battery, manufacturing an antireflection film on the surface of the battery, and manufacturing a nano array structure on the antireflection film. Wherein, citric acid is adopted: hydrogen peroxide: and (3-6) corroding the cap layer with the corrosion rate of 50-200 nm/min. And preparing the titanium oxide/silicon oxide antireflection film by adopting PECVD (plasma enhanced chemical vapor deposition), wherein the deposition rate is 5-50 nm/min. Adopting a nano-imprinting process to manufacture a nano-array structure;
and step S10, scribing, and dividing the inner cascade laser photovoltaic device. Wherein a grinding wheel scribing machine is adopted for scribing, the particle size of a scribing knife is 3-6 mu m, and the rotating speed is 30000-40000 r/min.
A forming process of an InP laser photovoltaic device with a 1064nm/1550nm waveband comprises the following steps:
step S01, preparing the active layer of the reverse InP-based laser battery by MOCVD epitaxy, and the specific process comprises the following steps:
s001, adopting an n-type doped InP substrate with a thickness of 200-600 μm and a doping concentration of 1 × 10 17 ~1×10 18 cm -3 ;
S002, epitaxially growing an InP buffer layer with the thickness of 50-100 nm;
s003, epitaxially growing an AlAs sacrificial layer with the thickness of 50-100 nm;
S004and epitaxially growing an n-type GaInAs cap layer with a thickness of 100-200 nm and a doping concentration of 1 × 10 18 ~1×10 19 cm -3 ;
S005, growing a first GaInAsP sub-battery by reverse epitaxy;
s006, epitaxially growing a tunneling junction;
s007, growing a second GaInAsP sub-battery through reverse epitaxy;
s008, epitaxially growing a p-type GaInAs cap layer with the thickness of 100-200 nm and the doping concentration of 1 multiplied by 10 18 ~1×10 19 cm -3 。
And step S02, preparing a patterned metal layer with the same size on the InP epitaxial wafer and the silicon oxide substrate by adopting a photoetching process, wherein the metal layer comprises an alignment mark and is used as a bonding metal layer and a battery lower electrode. Wherein, a vapor deposition process is adopted to prepare a metal layer Ti/Ag/Au, the evaporation rate is 5-50 nm/min, and the total thickness is 3-6 μm;
and step S03, aligning the InP epitaxial wafer with the patterned metal layer on the silicon oxide substrate through the alignment mark, and carrying out metal bonding. Wherein the bonding temperature is 200-400 ℃, the bonding pressure is 0.3-0.8 Mpa, and the bonding annealing time is 10-40 min;
and step S04, removing the InP substrate by adopting a substrate stripping multiplexing technology to complete the transfer of the epitaxial layer to the silicon oxide substrate. Wherein, the AlAs sacrificial layer is corroded by HF acid, the concentration of the HF acid is 10-25%, the corrosion temperature is 40-60 ℃, and the corrosion time is 5-30 h;
and step S05, photoetching a battery isolation groove pattern according to the patterned lower electrode by adopting a photoetching sleeve process. The isolation groove of the lower electrode bridge connection point is added under the condition that the interval between the photoetching isolation groove graph and the lower electrode graph is consistent;
and step S06, etching the isolation groove, completely etching the epitaxial active layer of the cell, and exposing the lower electrode cutting gap and the lower electrode bridging point. Etching all the epitaxial active layer materials of the cells in the isolation groove by adopting bromine-based etching liquid, wherein the etching rate is 100-800 nm/min;
s07, filling a passivation isolation groove with insulating glue, wherein the insulating glue is polyimide glue, and the curing temperature is 100-300 ℃;
and step S08, manufacturing an upper electrode on the surface of the battery by adopting a photoetching sleeve process, and manufacturing a bridging electrode to cross the insulating glue filled in the isolation groove to connect the upper electrode and the lower electrode of the sub-battery. Wherein, a vapor deposition process is adopted to prepare a metal layer Ti/Ag/Au, the evaporation rate is 5-50 nm/min, and the total thickness is 3-6 μm;
and S09, corroding the cap layer on the surface of the battery, manufacturing an antireflection film on the surface of the battery, and manufacturing a nano array structure on the antireflection film. Wherein, citric acid is adopted: hydrogen peroxide: and (3-6) corroding the cap layer with the corrosion rate of 50-200 nm/min. And preparing the titanium oxide/silicon oxide antireflection film by adopting PECVD (plasma enhanced chemical vapor deposition), wherein the deposition rate is 5-50 nm/min. Adopting a nano-imprinting process to manufacture a nano-array structure;
and step S10, scribing, and cutting the inner cascade laser photovoltaic device. Wherein a grinding wheel scribing machine is adopted for scribing, the particle size of a scribing knife is 3-6 mu m, and the rotating speed is 30000-40000 r/min.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modifications, equivalent variations and modifications made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (13)
1. A molding process of a laser photovoltaic device is characterized by comprising the following steps:
step S01, epitaxially preparing an active layer of the reverse III-V semiconductor laser battery on the first substrate;
step S02, preparing patterned metal layers with the same size on the epitaxial surface of the first substrate and the second substrate by adopting a photoetching process, wherein the metal layers comprise alignment marks and are used as bonding metal layers and lower electrodes of batteries;
step S03, aligning the epitaxial surface of the first substrate with the patterned metal layer on the second substrate through the alignment mark, and carrying out metal bonding;
step S04, removing the first substrate by adopting a substrate stripping multiplexing technology to complete the transfer of the epitaxial layer to the second substrate;
step S05, photoetching an isolation groove pattern according to the patterned lower electrode by adopting a photoetching sleeve process;
step S06, etching the isolation groove, completely etching the epitaxial active layer of the battery, and exposing the lower electrode cutting gap and the lower electrode bridging lead point;
step S07, filling the passivation isolation groove with insulating glue;
step S08, manufacturing an upper electrode on the surface of the battery by adopting a photoetching sleeve process, and manufacturing insulating glue for bridging the electrodes to cross the filling of the isolation grooves to connect the upper electrode and the lower electrode of the sub-battery;
step S09, corroding a cap layer on the surface of the battery, manufacturing an antireflection film on the surface of the battery, and manufacturing a nano array structure on the antireflection film;
and step S10, scribing, and cutting the inner cascade laser photovoltaic device.
2. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in the step S01, the reverse GaAs-based laser cell active layer is prepared by MOCVD epitaxy: the specific process comprises the following steps:
s101, adopting a GaAs substrate as a first substrate;
s102, epitaxially growing a GaInAs buffer layer;
s103, epitaxially growing an AlAs sacrificial layer;
s104, epitaxially growing a GaAs cap layer:
s105, growing a first Ga (in) As sub-battery in a reverse epitaxial mode;
s106, epitaxially growing a tunneling junction;
s107, growing a second Ga (in) As sub-battery in a reverse epitaxial mode;
and S108, epitaxially growing a GaAs cap layer.
3. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in step S01, the reverse InP-based laser cell active layer is prepared by MOCVD epitaxy: the specific process comprises the following steps:
s001, adopting an InP substrate as a first substrate;
s002, epitaxially growing an InP buffer layer;
s003, epitaxially growing an AlAs sacrificial layer;
s004, epitaxially growing a GaInAs cap layer;
s005, growing a first GaInAsP sub-battery by reverse epitaxy;
s006, epitaxially growing a tunneling junction;
s007, growing a second GaInAsP sub-battery through reverse epitaxy;
and S008, epitaxially growing a GaInAs cap layer.
4. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in the step S02, the second substrate is an insulating substrate, the substrate material is silicon oxide or polyimide or quartz, and the metal layer Ti/Ag/Au is prepared by adopting an evaporation process, wherein the evaporation rate is 5-50 nm/min.
5. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in the step S03, the bonding temperature is 200-400 ℃, the bonding pressure is 0.3-0.8 Mpa, and the bonding annealing time is 10-40 min.
6. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in step S04, the substrate lift-off multiplexing technique is: and corroding the AlAs sacrificial layer by using HF acid, wherein the concentration of the HF acid is 10-25%, the corrosion temperature is 40-60 ℃, and the corrosion time is 5-30 h.
7. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in step S05, the spacing between the patterned isolation trenches and the patterned bottom electrode is consistent, and isolation trenches for bottom electrode bridge contacts are added.
8. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in the step S06, bromine-based corrosive liquid is adopted to etch all the epitaxial active layer materials of the battery in the isolation groove until the lower electrode cutting gap and the lower electrode bridging point are exposed, and the etching rate is 100-800 nm/min.
9. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in the step S07, the insulating glue is polyimide glue, and the curing temperature is 100-300 ℃.
10. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in the step S08, a metal layer Ti/Ag/Au is prepared by an evaporation process, wherein the evaporation rate is 5-50 nm/min.
11. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in step S09, citric acid: hydrogen peroxide: and (3-6) corroding the cap layer with the corrosion rate of 50-200 nm/min.
12. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in the step S09, the titanium oxide/silicon oxide antireflection film is prepared by PECVD, the deposition rate is 5-50 nm/min, and the nano-array structure is manufactured by adopting a nano-imprinting process.
13. The molding process of the laser photovoltaic device according to claim 1, characterized in that: in the step S10, a grinding wheel scribing machine is adopted for scribing, the particle size of a scribing knife is 3-6 μm, and the rotating speed is 30000-40000 r/min.
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