CN105336796B - Double-side photic GaAs multijunction solar cells of inverted structure and preparation method thereof - Google Patents
Double-side photic GaAs multijunction solar cells of inverted structure and preparation method thereof Download PDFInfo
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- CN105336796B CN105336796B CN201510614489.6A CN201510614489A CN105336796B CN 105336796 B CN105336796 B CN 105336796B CN 201510614489 A CN201510614489 A CN 201510614489A CN 105336796 B CN105336796 B CN 105336796B
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- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- Y02E10/50—Photovoltaic [PV] energy
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Abstract
Double-side photic GaAs multijunction solar cells of inverted structure and preparation method thereof, it is related to GaAs multijunction solar cell production technical field, the present invention uses sandwich bonding pattern, front battery and reverse side battery independent each other is formed with the tow sides of same permanent substrate simultaneously, positive and negative battery can absorb light conversion electric energy, the present invention can effectively utilize incident each several part, reflection and the sunshine of scattering, two batteries work and add the electric output power of solar cell simultaneously, and the two works, is independent of each other simultaneously.Technique is simple, easy to operate, improves the electric transfer power of output of battery, compensate for losing effect of light source, improve the gravimetric specific power of battery, alleviates the delivery of rocket and the flight burden of satellite.
Description
Technical field
The present invention relates to GaAs multijunction solar cell production technical field.
Background technology
The solar cell of China is developed rapidly, and wherein GaAs solar cells are that aerospace industry carries key player.At present
GaAs multijunction solar cells mainly have using Ge and GaAs substrate formal dress multijunction solar cell, and inverted structure many knot sun
Battery, wherein being inverted multijunction solar cell because each junction battery band gap preferably matches full spectrum, contributes to sun light absorbs, makes
Its photoelectric transformation efficiency is obtained all the time far ahead of other solar cells, the favor of people is enjoyed.Although upside-down mounting solar cell turns
Changing that efficiency is higher, but because being bonded using about 2-3um Au, the weight increase 6-8% of cell piece, conversely to tie Ge substrate formal dress more
Efficiency of solar cell brings up to the 32% of upside-down mounting battery from 29%, and efficiency improves about 9%, from the point of view of contrast, the weight ratio of solar cell
It is very little that power is improved！
Detailed step is as follows：
1st, epitaxial growth：
Grow N-type GaAs cushion, GaInP etch stop layers, N-type successively on gaas substrates using MOCVD device
Battery, the second tunnel junctions, InGaAs bottoms battery and p-type in GaAs contact layers, GaInP tops battery, the first tunnel junctions, GaAs
InGaAs contact layers complete the growth of epitaxial wafer.
2nd, substrate is shifted：
The transfer Si substrates that conduction type is p-type are chosen, it is cleaned standby；The bottom battery back of battery epitaxial wafer and turn
Si substrate faces are moved, Ti, Pt and Au layers are deposited successively by electron beam respectively, then battery epitaxial wafer and transfer Si linings will be deposited
Bottom carries out metal bonding.
3rd, substrate desquamation：
The GaAs substrates on the battery epitaxial structure after metal bonding are removed using ammoniacal liquor, hydrogen peroxide corrosive liquid.
4th, electrode fabrication：
Using negative photoresist art lithography gate electrode line figure, with electron beam and the mode of thermal resistance vacuum evaporation, on top
Metal electrode is prepared on battery ohmic contact layer, and Top electrode will be completed by organic stripping and is made；In transfer Si substrate backs
Evaporation prepares bottom electrode.
5th, antireflective coating：
The cell piece of selective corrosion will be completed, TiO is deposited using the method for electron beam evaporation plating2/Al203Double-layer reflection-decreasing
Film.
6th, annealing, scribing, end face processing complete the making of upside-down mounting solar cell chip.
The product of formation is as shown in Figure 1：Have successively in the top of bottom electrode 21 substrate layer 22, metal bonding layer 23, one fall
Battery epitaxial layer 24, the antireflective coating 25 of dress, two Top electrodes 26 are conductively connected with battery epitaxial layer 24.
This current efficiency highest efficiency of GaInP/GaAs/InGaAs inverted triple-junctions solar cell is 32% or so, in light
Compose under AM 0, etalon optical power is 136.7mw/cm2, power output is about 43.74 mw/cm2Rate, already close to theoretical value.Due to
Sunshine can be reflected and scatter by atmosphere, and so many sunshines are not utilized, and are largely a kind of money
The waste in source, directly affects the electric output power of solar cell, moreover the sunshine of reflection and scattering is radiated at solar panel
The part back side can generate heat, and influence the service life of product.
It is now the conventional thinking for the power output for improving battery, exactly improves the electricity conversion of its battery to change
Cell body back side light part in space is confined and have ignored to gravimetric specific power, this thinking pattern.
The content of the invention
In view of the shortcomings of the prior art, the present invention seeks to propose a kind of to improve the output work of solar cell photoelectric conversion
Rate is so as to improve the double-side photic GaAs multijunction solar cells of the inverted structure of gravimetric specific power.
The present invention includes semi-insulating or insulation permanent substrate, and bonded layer is passed through respectively in the tow sides of the permanent substrate
Each connection positive battery epitaxial layer and anti-battery epitaxial layer, set positive battery Top electrode, anti-on the surface of positive battery epitaxial layer
The surface of battery epitaxial layer sets anti-battery Top electrode, sets and subtracts respectively on the surface of positive battery epitaxial layer and anti-battery epitaxial layer
Reflectance coating, the key exposed as positive battery bottom electrode, anti-battery bottom electrode is cut through in the tow sides of the permanent substrate respectively
Close layer.
Due to the insulating effect of permanent substrate, the present invention is formed with and born to be only simultaneously in the tow sides of same permanent substrate
Vertical front battery and reverse side battery, positive and negative battery can absorb light conversion electric energy, and the present invention can effectively utilize each several part
The sunshine of incidence, reflection and scattering, two batteries work and add the electric output power of solar cell simultaneously, and the two is while work
Make, be independent of each other.Further, since the present invention is only with a permanent substrate, solar cell gravimetric specific power is improved, mitigates empty
Between run with solar cell carrying burden.The Top electrode and bottom electrode of same battery are arranged in the same of permanent substrate by the present invention
Side, rather than the traditionally vertical stratification of lower output, enable two batteries to work independently without interruption, also beneficial to recognition, side
Just the connection of lead.
In addition, in order that diamond dicing saw can be normally cut in tow sides solar cell cutting groove, reduction is electric
Chamber chip product failure and bad, positive battery Top electrode of the present invention and anti-battery of performance caused by the difference of cutting position
Top electrode is arranged symmetrically in the tow sides of the permanent substrate.
Similarly, the positive battery bottom electrode and anti-battery bottom electrode are arranged symmetrically in the tow sides of the permanent substrate.
Antireflective coating of the present invention can be TiO2/Ta2O5/Al2O3, or TiO2/Ta2O5/SiO2, or TiO2/Si3N4/
Al2O3, or TiO2/Si3N4/ SiO2One kind in three-decker.Ta2O5、Si3N4Refractive index is 2.0, is relatively adapted to trilamellar membrane
System, but Ta2O5The easy splash in source in electron beam evaporation plating, stability is poor, is unfavorable for bulk production；Al2O3Refractive index is 1.6,
SiO2Refractive index is 1.46, according to optical principle, and Al can be compared by dredging the small SiO2 of the close refractive index of light by light2O3Refraction angle is small, therefore
TiO2/Si3N4/ SiO2Antireflective coating reflectivity is more excellent.
It is another object of the present invention to the preparation side for the double-side photic GaAs multijunction solar cells for proposing above inverted structure
Method.
The present invention comprises the following steps；
1）Epitaxial wafer grows:Routinely technique, the slow of N-type GaAs is grown using MOCVD successively on interim GaAs substrates
Rush battery, the second tunnelling in layer, GaInP etch stop layers, N-type GaAs contact layers, GaInP tops battery, the first tunnel junctions, GaAs
Knot, InGaAs bottoms battery and p-type InGaAs contact layers complete complete battery epitaxial wafer growth；
2）Substrate is shifted：Pass through metal bonding layer back bonding respectively on semi-insulating or insulation permanent substrate positive and negative surface
Respectively there are the sandwich style semi-products of an epitaxial layer in the middle of battery epitaxial wafer, formation for permanent substrate both sides；
3）Substrate desquamation：The temporary substrates and N-type GaAs of the epitaxial layer positioned at sandwich style semi-products both sides are removed respectively
Cushion, until exposing the GaInP etch stop layers of each epitaxial layer；
4）Top electrode makes：After the GaInP etch stop layers of each epitaxial layer are removed, in sandwich style semi-products both sides point
Zhi Zuo not positive battery Top electrode and anti-battery Top electrode；
5）Antireflective coating makes：First the N-type GaAs of each epitaxial layer selectively beyond each Top electrode of erosion removal connects
Contact layer, then each epi-layer surface beyond each Top electrode prepare antireflective coating；
6）Annealing forms Ohmic contact；
7）Bottom electrode makes：Etched on each epitaxial layer, until exposed portion metal bonding layer；
8）Scribing；
9）Section corrodes.
The present invention uses sandwich bonding pattern, and technique is simple, easy to operate, using only the mode being once bonded, you can
Two independent battery backings are privately bonded at conductive and radiated on preferable substrate.Positive and negative is rotten by synchronous selectivity
The a series of device technologies such as erosion, antireflective coating etching, scribing and section corrosion, completion is two-sided can to absorb the electricity of sunshine
Pond, the battery of such positive and negative works simultaneously, the electric transfer power of output, compensate for losing effect of light source, improves the electricity
The gravimetric specific power in pond, alleviates the delivery of rocket and the flight burden of satellite.
Further, when substrate is shifted, it is respectively adopted respectively in the tow sides of the permanent substrate Jing Guo cleaning treatment
Electron beam evaporation plating bonded layer, uses electron beam evaporation plating bonded layer, then pass through evaporation in the front of the epitaxial wafer with temporary substrates
Two panels there is the epitaxial wafer of temporary substrates to be attached to the tow sides in permanent substrate respectively by bonded layer, then pass through heating, pressurization
Two wafer bondings are transferred in permanent substrate by method.Reached by stripping and turn the inverted cell piece of two panels,
So formal dress can not grow battery in GaInP top batteries (1.85eV), GaAs（1.40 eV）, InGaAs bottoms battery (1.0 eV)
Structure can be grown by upside-down mounting, be bonded transfer to be formed, and effectively be make use of 300~1800nm solar spectrums, improved light
Photoelectric transformation efficiency.
When Top electrode makes, first using negative photoresist art lithography gate electrode line figure, then with electron beam and thermal resistance
The mode of vacuum evaporation, is less than under conditions of 100 DEG C in evaporation cavity temperature, Top electrode is prepared respectively on two epitaxial layers,
And positive battery Top electrode and anti-battery Top electrode are formed by organic stripping.Top electrode is thicker due to deposited metal film, typically 3
~4um, and cell body material is oxidizable and the reason for be corroded, it is impossible to using the method for etching, mainly using lift-off
Method, required electrode pattern is first produced with negative photoresist, then in patterned surface deposited metal layer, last organic dissolution
Photoresist, strips down unwanted metal part, can so form precision in ± 1um metal electrodes, be conducive to electrode
Uniformity, improve battery current density.
In order to form effective symmetrical effect, the present invention first makes front battery Top electrode, then when Top electrode makes
Reverse side battery Top electrode is made to the symmetrical alignment of the permanent substrate another side again.
Similarly, when bottom electrode makes, using automatic litho machine positive and negative CCD images positive and negative the two of the permanent substrate
Electrode pattern is made in face of position alignment, using wet method or dry etching, the good position of alignment is etched through two metals respectively
Bonded layer.
Brief description of the drawings
Fig. 1 is battery epitaxial wafer structural representation.
Fig. 2 is the structural representation of prior art products.
Fig. 3 is structural representation when this bright product bottom electrode is not formed.
Fig. 4 is the structural representation of this bright product.
Fig. 5 is Fig. 4 top view.
Fig. 6 is Fig. 4 upward view.
Embodiment
First, reference picture 2,3,4,5,6 are described in detail production technology of the present invention：
1st, epitaxial wafer grows：
Grow N-type GaAs cushion 11, GaInP corrosion successively on 350um GaAs substrates 10 using MOCVD device
Battery 16, the second tunnel junctions in cutoff layer 12, N-type GaAs contact layers 13, GaInP tops battery 14, the first tunnel junctions 15, GaAs
17th, InGaAs bottoms battery 18 and p-type InGaAs contact layers 19, complete the outer layer growth of the epitaxial wafer with temporary substrates.Such as
Shown in Fig. 2.
2nd, battery epitaxial wafer bonded layer is deposited：Choose the above-mentioned battery epitaxial wafer laser marking of two panels to be numbered, use third
Ketone, isopropanol organic ultrasonic cleaning 10Min, dry 15Min, on p-type InGaAs contact layers 19 respectively by electron beam successively
Ti, Pt and Au metal bonding layer is deposited, gross thickness is not less than 1um.
3rd, permanent substrate bonded layer is deposited：
The Si SI-substrates 35 of a piece of thick 200um twin polishings and tow sides Jing Guo oxidation processes are chosen, through organic
Ultrasonic 10Min, 15Min is dried, and the tow sides of Si SI-substrates 35 after the drying are steamed successively by electron beam respectively
Ti, Pt and Au metal bonding layer 34,36 is plated, the gross thickness in each face is not less than 1um.
Above Si SI-substrates 35 can use any one of conventional GaAs substrates, Sapphire Substrate or SiC substrate
Substitute.
4th, substrate is shifted：
The epitaxial wafer after Ti, Pt and Au metal bonding layer and blocks of evaporation Ti, Pt and Au metal is deposited in the two panels
The tow sides flip-over type of the Si SI-substrates 35 of bonded layer 34,36 is combined, by high-temperature heating to 400 DEG C, pressurization
To 7000kg/cm2Sandwich bonding 20min is carried out, two cell piece is firmly adhered to Si substrates, forms middle
There are the sandwich style semi-products of positive battery epitaxial layer 37 and anti-battery epitaxial layer 33 respectively for the both sides of permanent substrate 35.
5th, substrate desquamation：
Ammoniacal liquor and hydrogen peroxide are mixed with 1: 10 volume ratio, mixed solution is formed.The immersion of sandwich style semi-products is mixed
Close in solution, the temporary substrates 10 and N-type on sandwich style semi-products on positive and negative battery epitaxial layer 33,37 are removed through 30min
GaAs cushion 11, exposes GaInP etch stop layers 12, and rinses, is dehydrated by QDR, dries stand-by.
6th, Top electrode makes：
It is 1 by the sandwich style semi-products immersion after substrate desquamation is completed by volume ratio:2 hydrochloric acid and phosphoric acid mixed solution
Middle removal GaInP etch stop layers 12.
Clean, after QDR cleanings are spin-dried for, applied using negative photo adhesive process through gold-tinted by acetone, alcohol organic ultrasonic again
The gate electrode line figure such as glue, photoetching, development, with electron beam and the mode of thermal resistance vacuum evaporation, in the front of Si SI-substrates
Battery epitaxial layer 37 on prepare metal electrode, and made by organic stripping by front battery Top electrode 39 is completed.
Equally, clean, after QDR cleanings are spin-dried for, applied on the surface of positive battery epitaxial layer 37 by acetone, alcohol organic ultrasonic
Negative photoresist, using automatic photoetching motor spindle CCD images to the face battery alignment, to ensure tow sides Top electrode same
On vertical line, gate electrode line graphic making is completed；With electron beam and the mode of thermal resistance vacuum evaporation, in the anti-of Si SI-substrates
Metal electrode is prepared on battery epitaxial layer 33, and is made by organic stripping by reverse side battery Top electrode 31 is completed.
The semi-products structure of formation is as shown in Figure 3.
7th, selective corrosion：
Citric acid, hydrogen peroxide and water are mixed with 1: 2: 2 volume ratio, mixed solution is formed.Above semi-products are immersed
In mixed solution, the N-type beyond front battery Top electrode 39 and reverse side battery Top electrode 31 is selectively etched at 40 DEG C
GaAs contact layers 13, are rinsed by QDR, are spin-dried for stand-by.
8th, antireflective coating makes：
Positive electricity of the semi-products of selective corrosion using the method for electron beam beyond front battery Top electrode 39 will be completed
TiO is deposited in the surface of pond epitaxial layer 372/Si3N4/ SiO2Double-layer reflection reducing coating 38.Anti- electricity beyond reverse side battery Top electrode 31
TiO is deposited in the surface of pond epitaxial layer 332/Si3N4/ SiO2Double-layer reflection reducing coating 32.
Wherein, TiO2Thickness 50nm, Si3N4/ thickness 25nm, SiO2Thickness 95nm, and make by way of alignment figure
The antireflective coating etching opening at electrode bonding wire position is easy to weld, tested.
Above antireflective coating can also use TiO2/Ta2O5/Al2O3, or TiO2/Ta2O5/SiO2, or TiO2/Si3N4/
Al2O3In one kind.
9th, anneal：
Using 400 DEG C of high temperature to the semi-products annealing 20min Jing Guo step 8, good Ohmic contact is formed.
10th, bottom electrode makes：
Positive-tone photo is used respectively in the positive battery epitaxial layer 37 of the semi-products by annealing and the anti-surface of battery epitaxial layer 33
Adhesive process gluing, symmetrically alignment, development, and use 1:1:The solution such as 3 phosphoric acid, hydrogen peroxide and water miscible fluid and hydrochloric acid enters
Row etching, alignment is got well and exposes 1x7mm2The battery epitaxial layer at position ends through metal bonding layer 36,34 respectively.
The metal bonding layer 36 is positive battery bottom electrode, and metal bonding layer 34 is anti-battery bottom electrode.As shown in Figure 4.
11st, scribing：
In the protection of positive and negative battery ARC surface coatings, cut or be cut by laser using diamond blade and battery chip is split,
Non-electrical pool area Partial Resection is left into completed cell chip.
12nd, end face corrodes
Citric acid, hydrogen peroxide and water are mixed with 1: 2: 2 volume ratio, mixed solution is formed.Existed using the mixed solution
3~5min is impregnated at 40 DEG C, by well cutting battery chip side etch cleaning cutting residue particles, and cleaning of removing photoresist completes described
The making of double-side cell.
Critical process of the present invention is：The permanent substrate Si for being bonding is that oxidation processes are passed through and two-sided in positive and negative two surface
Polishing, it is ensured that battery current will not down perpendicular flow；Secondly, battery epitaxial layer is cut through by key using the method for chemical etching
Layer is closed as bottom electrode, positive and negative electrode is in the horizontal output of substrate Si the same side.Further, to ensure tow sides battery
Electrode is on same vertical line, it is necessary to using automatic litho machine positive and negative CCD image electrode alignment alignments, so that cutting scribing
In positive and negative battery scribe line.
2nd, product structure and performance characteristics：
As shown in figure 4, the product being made includes permanent substrate 35, bonding is passed through respectively in the tow sides of permanent substrate 35
Layer 36,34 each connects positive battery epitaxial layer 37 and anti-battery epitaxial layer 33, and positive electricity is set on the surface of positive battery epitaxial layer 37
Pond Top electrode 39, sets anti-battery Top electrode 31, in positive battery epitaxial layer 37 and anti-battery on the surface of anti-battery epitaxial layer 33
The surface of epitaxial layer 33 sets antireflective coating 38,32 respectively, is cut through respectively in the tow sides of the permanent substrate 35 and exposes work
For positive battery bottom electrode, the bonded layer 36,34 of anti-battery bottom electrode.
Also, positive battery Top electrode 39 and anti-battery Top electrode 31 are arranged symmetrically in the tow sides of permanent substrate 35, just
Battery bottom electrode and anti-battery bottom electrode are arranged symmetrically in the tow sides of the permanent substrate 35.
Fig. 5 is Fig. 4 top view, it is seen that：On the same surface of positive battery epitaxial layer 37, one positive electricity can be not only set
Pond Top electrode 39, can also not only set an anti-battery bottom electrode.
Fig. 6 is Fig. 4 upward view, it is seen that：One anti-electricity can be not only set on the same anti-surface of battery epitaxial layer 33
Pond Top electrode 31, also can not only set an anti-battery bottom electrode.
Because two batteries of the positive and negative of the present invention work simultaneously, power output, will effectively improve solar cell respectively
Generating efficiency；In addition, two batteries are used in conjunction with same substrate Si piece, and it is so indirect to reduce substrate weight, improve sun electricity
The gravimetric specific power in pond.
Claims (3)
1. the preparation method of the double-side photic GaAs multijunction solar cells of inverted structure, including prepare the extension with temporary substrates
Piece, substrate transfer, substrate desquamation, Top electrode making, antireflective coating making, annealing form Ohmic contact, bottom electrode and make, draw
Piece, section corrosion step；It is characterized in that：
When substrate is shifted, metal bonding layer back bonding electricity is passed through respectively on semi-insulating or insulation permanent substrate positive and negative surface
Respectively there are the sandwich style semi-products of an epitaxial layer in the middle of pond epitaxial wafer, formation for permanent substrate both sides；
In substrate desquamation, the temporary substrates and N-type GaAs of the epitaxial layer positioned at sandwich style semi-products both sides are removed respectively
Cushion, until exposing the GaInP etch stop layers of each epitaxial layer；
When Top electrode makes, after the GaInP etch stop layers of each epitaxial layer are removed, in sandwich style semi-products both sides difference
Make positive battery Top electrode and anti-battery Top electrode；
When antireflective coating makes, the first N-type GaAs contacts of each epitaxial layer selectively beyond each Top electrode of erosion removal
Layer, then each epi-layer surface beyond each Top electrode prepare antireflective coating；
When bottom electrode makes, etched on each epitaxial layer, until exposed portion metal bonding layer；
When Top electrode makes, front battery Top electrode is first made, then symmetrically set is scribed to the permanent substrate another side again
Make reverse side battery Top electrode；
When bottom electrode makes, aligned and covered in the tow sides of the permanent substrate using automatic litho machine positive and negative CCD images
Scribe and make electrode pattern, using wet method or dry etching, the good position of alignment is etched through two metal bonding layers respectively.
2. preparation method according to claim 1, it is characterised in that when substrate is shifted, is passing through cleaning treatment forever respectively
Electron beam evaporation plating bonded layer is respectively adopted in the tow sides of long substrate, and electronics is used in the front of the epitaxial wafer with temporary substrates
Bonded layer is deposited in beam, then is attached to the epitaxial wafer that two panels has temporary substrates in permanent substrate just respectively by the way that bonded layer is deposited
Anti- two sides, then two wafer bondings are transferred in permanent substrate by heating, pressure method.
3. preparation method according to claim 1, it is characterised in that when Top electrode makes, first using negative photoresist work
Skill photoetching gate electrode line figure, then with electron beam and the mode of thermal resistance vacuum evaporation, it is less than 100 DEG C of bar in evaporation cavity temperature
Under part, Top electrode is prepared respectively on two epitaxial layers, and form electric in positive battery Top electrode and anti-battery by organic stripping
Pole.
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| CN109148622A (en) * | 2018-08-15 | 2019-01-04 | 中山德华芯片技术有限公司 | A kind of two-sided high performance solar batteries and preparation method thereof |
| CN111276559B (en) * | 2020-02-17 | 2022-07-26 | 扬州乾照光电有限公司 | Solar cell structure and preparation method thereof |
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