CN102637826A - Large-area organic solar cell structure and preparation method thereof - Google Patents
Large-area organic solar cell structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a large-area organic solar cell structure and a preparation method for the large-area organic solar cell structure, and relates to the technical field of organic photoelectric devices. The problem that as the existing large-area organic solar cell adopts a transparent metal oxide as a hole collecting electrode layer of a device, the electric resistance of the hole collecting electrode layer is high, and further the power conversion efficiency of a large-area device is lowered is solved. The large-area organic solar cell structure comprises a substrate, the hole collecting electrode layer, a metal grid auxiliary electrode layer, an anode buffer layer, an organic optical activity layer, a cathode buffer layer and an electronic collecting electrode layer, wherein the hole collecting electrode layer is deposited by adoption of a direct-current magnetron sputtering method, the metal grid auxiliary electrode layer firstly is deposited one layer of metal film by adoption of the direct-current magnetron sputtering method, and then the metal film is etched into an auxiliary electrode with a specific pattern by adoption of a wet etching technology. According to the large-area organic solar cell structure and the preparation method, the serial electric resistance of the large-area organic solar cell can be greatly lowered, so that the power conversion efficiency of the device is improved.
Description
Technical field
The present invention relates to the organic electro-optic device technical field, be specifically related to a kind of large tracts of land organic solar energy cell structure and preparation method thereof.
Background technology
Solar cell is the device that the luminous energy of solar radiation is converted into electric energy.Research at present with most widely used be inorganic silica-based (comprising monocrystalline silicon, polysilicon and amorphous silicon) solar cell, but the preparation technology of complicacy, high cost have limited its extensive use.Organic solar batteries is in light weight because of it, technology is simple, cost is low, material is easy to get and performance is easy to regulation and control, can be integrated in large tracts of land and the first-class advantage of flexible substrate receives extensive concern.The course of work of organic solar batteries can summarize as follows: under illumination; The photon energy that organic photoactive layer in the device absorbs irradiation produces photoproduction exciton (electron-hole pair); The photoproduction exciton decomposes generation free carrier (electronics and hole); Electronics and hole finally form electric current respectively to the diffusion of electronic collection electrode layer and hole passive electrode layer and be collected in external circuit.Hence one can see that, and the collection in electronics and hole is one of key factor of decision device power conversion efficiency.
The power conversion efficiency of the organic solar batteries of report has reached 8% at present, but these efficient are (to be generally less than 20mm at small size
2) the principle device on obtain.And organic solar batteries will be realized practicability, must obtain high efficiency broad area device.Present most of organic solar batteries adopts the transparent conductive metal oxide, and (indium tin oxides, ITO), as the hole passive electrode layer of device, used conducting metal oxide face resistance is big (generally greater than 10 Ω) like indium tin oxide.When adopting the transparent conductive metal oxide as the hole passive electrode layer of large tracts of land organic solar batteries; The resistance of transparent conductive metal oxide makes the series resistance of broad area device increase with device area and enlarges markedly; Cause photo-generated carrier in collection process, to lose increase, cause the power conversion efficiency of broad area device to increase decline rapidly with device area.In order to improve the power conversion efficiency of large tracts of land organic solar batteries; The resistance that effectively reduces hole passive electrode layer is one of necessary approach, such as adopting vacuum thermal evaporation process deposits deposition techniques layer of metal Al auxiliary electrode around the passive electrode layer in the hole of device.This method has certain effect on the power conversion efficiency than the small size device relatively in raising, but this method can't reduce the resistance of effective area inner cavity passive electrode layer in the broad area device.
Summary of the invention
The present invention adopts the hole passive electrode layer of transparent metal oxide as device for solving existing large tracts of land organic solar batteries; Cause the resistance of hole passive electrode layer bigger; And then the problem that reduces of the power conversion efficiency that causes broad area device, a kind of large tracts of land organic solar energy cell structure and preparation method thereof is provided.
A kind of large tracts of land organic solar energy cell structure, this structure comprise substrate layer, hole passive electrode layer, metal grill auxiliary electrode layer, anode buffer layer, organic photoactive layer, cathode buffer layer and electronic collection electrode layer; Growth hole passive electrode layer on the said substrate layer; Depositing metal films on the passive electrode layer of said hole; Etching metal grill auxiliary electrode layer on metallic film, on said metal grill auxiliary electrode layer, grow successively anode buffer layer, organic photoactive layer, cathode buffer layer and electronic collection electrode layer; The thickness of said metal grill auxiliary electrode layer is 20-200nm, and the material of metal grill auxiliary electrode layer is Metal Cr or Ag.
Based on a kind of preparation method of large tracts of land organic solar energy cell structure, this method is realized by following steps:
Step 1, on substrate, adopt direct current magnetron sputtering process deposition hole passive electrode layer;
Step 3, at the described metal grill auxiliary electrode layer of step 2 deposition anode resilient coating, organic photoactive layer and cathode buffer layer successively;
Step 4, on the described cathode buffer layer of step 3, adopt vacuum thermal evaporation process deposits electronic collection electrode layer.
Beneficial effect of the present invention: large tracts of land organic solar energy cell structure of the present invention has added the metal grill auxiliary electrode layer on the passive electrode layer of hole; Can effectively reduce the resistance of hole passive electrode layer; Reduce the loss of photo-generated carrier in collection process; Improve the collection efficiency of photo-generated carrier, improve short circuit current, fill factor, curve factor and the power conversion efficiency of device.
Description of drawings
Fig. 1 is the sketch map of large tracts of land organic solar energy cell structure of the present invention, among the figure 1, substrate, and 2, hole passive electrode layer; 3, metal grill auxiliary electrode layer, 4, anode buffer layer, 5, the organic photoactive layer; 6, cathode buffer layer, 7, the electronic collection electrode layer;
Fig. 2 is the metal auxiliary electrode sketch map in the existing standard device 2;
The metal grill auxiliary electrode sketch map that Fig. 3 is adopted for the device of the present invention 1 described in the embodiment three;
The metal grill auxiliary electrode sketch map that Fig. 4 is adopted for the device of the present invention 2 described in the embodiment three;
Fig. 5 is the I-V characteristic curve sketch map of existing standard device described in Fig. 2 and device of the present invention.
Embodiment
Embodiment one, combination Fig. 1 explain this execution mode; A kind of large tracts of land organic solar energy cell structure, this structure comprise substrate layer 1, hole passive electrode layer 2, metal grill auxiliary electrode layer 3, anode buffer layer 4, organic photoactive layer 5, cathode buffer layer 6 and electronic collection electrode layer 7; Growth hole passive electrode layer 2 on the said substrate layer 1; Depositing metal films on the passive electrode layer 2 of said hole; Etching metal grill auxiliary electrode layer 3 on metallic film, on said metal grill auxiliary electrode layer 3, grow successively anode buffer layer 4, organic photoactive layer 5, cathode buffer layer 6 and electronic collection electrode layer 7; The thickness of said metal grill auxiliary electrode layer 3 is 20-200nm, and the material of metal grill auxiliary electrode layer 3 is Metal Cr or Ag.
The described metal grill electrode layer of this execution mode is made up of the auxiliary electrode (outer lines) around the hole passive electrode layer 2 and hole passive electrode layer 2 inner auxiliary electrode (interior lines) two parts.
Substrate layer 1 described in this execution mode adopts glass or polymeric material substrate, as polyethylene (polyethylene, PE), poly terephthalic acid ethylene glycol (polythylene terephthalate, PET); Hole passive electrode layer 2 adopts the transparent conductive metal oxide; Like indium tin oxide (indium tin oxides; ITO), the fluorine tin-oxide (fluorine-doped tin oxide, FTO), the aluminium zinc oxide (aluminum-doped zinc oxide, AZO); Metal grill auxiliary electrode layer 3 materials adopt Metal Cr or Ag; Anode buffer layer 4 adopts metal oxide, like molybdenum trioxide (MoO
3), tungstic acid (WO
3), vanadic oxide (V
2O
5), or adopt organic substance, as gather (3; 4-enedioxy thiophene): (poly (3 to gather (styrene sulfonic acid); 4-ethylenedioxythiophene): polystrrenesulfonate, PEDOT:PSS), polyethylene oxide (polyethylene oxide, PEO); Organic photoactive layer 5 adopts metal phthalocyanine complexs, as CuPc (copper phthalocyanine, CuPc), Phthalocyanine Zinc (zinc phthalocyanine; ZnPc), phthalocyanine tin (tin phthalocyanine, SnPc), or polythiofuran derivative; Like P3HT (poly (3-hexylthiophene)); Or polystyrene derivative, as MEH-PPV (poly (2-methoxy-5-2 '-ethylhexyloxy)-1,4-phenylenevinylene; Or fullerene derivate; (one or more materials in [6,6]-phenylC61-butyricacidmethylester), organic photoactive layer 5 can adopt individual layer, multilayer or mixed layer structure like C60, PCBM; Cathode buffer layer 6 adopts organic substances, as BCP (bathocuproine), Bphen (4,7-diphenyl-1,10-phenanthroline), Alq
3(tris (8-hydroxyquinoline) aluminum), Alq
3: Mg, Bphen:Li, or adopt metal oxide, like titanium dioxide (TiO
2), manganese oxide (MnO); Electronic collection electrode layer 7 adopts metal A l, metal Ca, Mg:Ag alloy.
The thickness of the described substrate layer 1 of this execution mode is 0.1-2mm; The thickness of hole passive electrode layer 2 is 20-400nm; The thickness of anode buffer layer 4 is 1-100nm; The thickness of organic photoactive layer 5 is 20-500nm; The thickness of cathode buffer layer 6 is 0.5-50nm; The thickness of electronic collection electrode layer 7 is 10-200nm.
Embodiment two, this execution mode are the preparation method of embodiment one described a kind of large tracts of land organic solar energy cell structure, and the implementation procedure of this method is:
At first, on substrate, adopt direct current magnetron sputtering process deposition hole passive electrode layer 2;
Secondly, on hole passive electrode layer 2, adopt direct current magnetron sputtering process deposition layer of metal film, adopt wet-etching technology metallic film to be etched into the metal grill auxiliary electrode layer 3 of specific pattern;
Then, deposition anode resilient coating 4, organic photoactive layer 5, cathode buffer layer 6 successively, more than each layer can adopt vacuum thermal evaporation technology or solution spin coating proceeding deposition;
At last, on cathode buffer layer 6, adopt vacuum thermal evaporation process deposits electronic collection electrode layer 7.
The metal grill auxiliary electrode layer 3 of the specific pattern described in this execution mode can be rectangle, square, triangle pattern etc.Described metal grill auxiliary electrode layer 3 is made up of auxiliary electrode (outer lines) and inner auxiliary electrode (interior lines) two parts around the hole passive electrode layer 2.The thickness of metal grill auxiliary electrode layer 3 is 20-200nm; Metal grill auxiliary electrode layer 3 line thickness are 0.1-2mm, and outer lines width of auxiliary electrode and interior line thickness can equate.
Substrate layer 1 described in this execution mode adopts glass or polymeric material substrate, like PE, PET; Hole passive electrode layer 2 adopts the transparent conductive metal oxide, like ITO, FTO, AZO; Metal grill auxiliary electrode layer 3 materials adopt Cr or Ag; Anode buffer layer 4 adopts metal oxide, like MoO
3, WO
3, V
2O
5, or adopt organic substance, like PEDOT:PSS, PEO; Organic photoactive layer 5 adopts metal phthalocyanine complex, like CuPc, ZnPc, SnPc, or polythiofuran derivative; Like P3HT; Or polystyrene derivative, like MEH-PPV, or fullerene derivate; Like one or more materials among C60, the PCBM, organic photoactive layer 5 can adopt individual layer, multilayer or mixed layer structure; Cathode buffer layer 6 adopts organic substance, like BCP, Bphen, Alq
3, Alq
3: Mg, Bphen:Li, or adopt metal oxide, like TiO
2, MnO; Electronic collection electrode layer 7 adopts Al, Ca or Mg:Ag alloy.
The thickness of the described substrate layer 1 of this execution mode is 0.1-2mm; The thickness of hole passive electrode layer 2 is 20-400nm; The thickness of anode buffer layer 4 is 1-100nm; The thickness of organic photoactive layer 5 is 20-500nm; The thickness of cathode buffer layer 6 is 0.5-50nm; The thickness of electronic collection electrode layer 7 is 10-200nm.
Embodiment three, combination Fig. 3 and Fig. 5 explain this execution mode; This execution mode is the preparation method's of embodiment two described a kind of large tracts of land organic solar energy cell structures embodiment: present embodiment adopts execution mode one described battery structure of the present invention
The glass that adopts 1.2mm behind the clean substrate layer 1, adopts direct current magnetron sputtering process on substrate layer 1, to deposit ITO as hole passive electrode layer 2 as substrate layer 1, and thickness is 300nm; Adopt direct current magnetron sputtering process plated metal Cr layer on hole passive electrode layer 2, thickness is 50nm; Adopt wet-etching technology that the Cr metal level is etched into grid auxiliary electrode structure as shown in Figure 3, obtain metal grill auxiliary electrode layer 3, wherein the outer lines width 3-1 of Cr metal grill auxiliary electrode layer 3 and interior line thickness 3-2 are respectively 1mm and 0.2mm; On hole passive electrode layer 2 and metal grill auxiliary electrode layer 3, deposit MoO
3As anode buffer layer 4, thickness is 5nm; On anode buffer layer 4, deposit 30nm CuPc and 40nmC60 successively as organic photoactive layer 5; Deposition Bphen is as cathode buffer layer 6 on organic photoactive layer 5, and thickness is 8nm; Plated metal Al is as electronic collection electrode layer 7 on cathode buffer layer 6 at last, and thickness is 100nm; Above anode buffer layer 4, organic photoactive layer 5, cathode buffer layer 6 all adopts vacuum thermal evaporation process deposits technology with electronic collection electrode layer 7, and vacuum degree is about 5 * 10
-4Pa.The I-V characteristic curve of device 1 of the present invention adopts Keithley 2400 digital source tables to measure, and test is 100mW/cm at power
2Xenon lamp irradiation under carry out.All measurements are all carried out under atmospheric environment.Measured I-V characteristic curve is the curve of device 1 correspondence of the present invention among Fig. 5.By knowing among the figure; The open circuit voltage of device 1 of the present invention is suitable with existing standard device 2 with existing standard device 1, but the short circuit current of device of the present invention 1, fill factor, curve factor and power conversion efficiency are compared all with existing standard device 2 with existing standard device 1 and be significantly increased.
Embodiment four, combination Fig. 4 and Fig. 5 explain this execution mode; This execution mode is the preparation method's of embodiment two described a kind of large tracts of land organic solar energy cell structures embodiment: present embodiment adopts execution mode one described battery structure of the present invention
The glass that adopts 1.2mm behind the clean substrate layer 1, adopts direct current magnetron sputtering process on substrate layer 1, to deposit ITO as hole passive electrode layer 2 as substrate layer 1, and thickness is 300nm; Adopt direct current magnetron sputtering process plated metal Cr layer on hole passive electrode layer 2, thickness is 50nm; Adopt wet-etching technology that the Cr metal level is etched into grid auxiliary electrode structure as shown in Figure 4, obtain metal grill auxiliary electrode layer 3, wherein the outer lines width 3-1 of Cr metal grill auxiliary electrode layer 3 and interior line thickness 3-2 are respectively 1mm and 0.2mm; On hole passive electrode layer 2 and metal grill auxiliary electrode layer 3, deposit MoO
3As anode buffer layer 4, thickness is 5nm; On anode buffer layer 4, deposit 30nm CuPc and 40nmC60 successively as organic photoactive layer 5; Deposition Bphen is as cathode buffer layer 6 on organic photoactive layer 5, and thickness is 8nm; Plated metal Al is as electronic collection electrode layer 7 on cathode buffer layer 6 at last, and thickness is 100nm; Above anode buffer layer 4, organic photoactive layer 5, cathode buffer layer 6 all adopts vacuum thermal evaporation process deposits technology with electronic collection electrode layer 7, and vacuum degree is about 5 * 10
-4Pa.The I-V characteristic curve of device 2 of the present invention adopts Keithley 2400 digital source tables to measure, and test is 100mW/cm at power
2Xenon lamp irradiation under carry out.All measurements are all carried out under atmospheric environment.Measured I-V characteristic curve is the curve of device 2 correspondences of the present invention among Fig. 5.By knowing among the figure; The open circuit voltage of device 2 of the present invention is suitable with existing standard device 2 with existing standard device 1, but the short circuit current of device of the present invention 2, fill factor, curve factor and power conversion efficiency are compared all with existing standard device 2 with existing standard device 1 and be significantly increased.
In conjunction with Fig. 5, all devices all adopt thickness be 1.2mm glass as substrate layer 1, thickness be the ITO of 300nm as hole passive electrode layer 2, the structure of existing standard device 1 is ITO/MoO
3(5nm)/and CuPc (30nm)/C60 (40nm)/Bphen (8nm)/Al (100nm), the structure of existing standard device 2, device of the present invention 1 and device of the present invention 2 is ITO/Cr (50nm)/MoO
3(5nm)/CuPc (30nm)/C60 (40nm)/Bphen (8nm)/Al (100nm).Wherein, the auxiliary electrode structure of existing standard device 2, device of the present invention 1 and device of the present invention 2 is respectively like Fig. 2, Fig. 3 and shown in Figure 4.
Table 1 is that the performance of existing standard device 1, existing standard device 2 and device of the present invention 1, device of the present invention 2 compares.The effective area of existing standard device 1, existing standard device 2 and device of the present invention 1, device 2 (being defined as the cross section area of hole passive electrode layer 2 and electronic collection electrode layer 7) is 30 * 30mm
2, the test of the current-voltage of device (I-V) characteristic curve is 100mW/cm at power
2Xenon lamp irradiation under carry out, the performance test of all devices is carried out under the identical conditions in atmospheric environment.
Table 1
Claims (10)
1. large tracts of land organic solar energy cell structure, this structure comprises substrate layer (1), hole passive electrode layer (2), metal grill auxiliary electrode layer (3), anode buffer layer (4), organic photoactive layer (5), cathode buffer layer (6) and electronic collection electrode layer (7); Said substrate layer (1) is gone up growth hole passive electrode layer (2); Said hole passive electrode layer (2) is gone up depositing metal films; It is characterized in that; Etching metal grill auxiliary electrode layer (3) on metallic film, the anode buffer layer (4) of on said metal grill auxiliary electrode layer (3), growing successively, organic photoactive layer (5), cathode buffer layer (6) and electronic collection electrode layer (7); The thickness of said metal grill auxiliary electrode layer (3) is 20-200nm, and the material of metal grill auxiliary electrode layer (3) is Metal Cr or Ag.
2. a kind of large tracts of land organic solar energy cell structure according to claim 1 is characterized in that, the material of said substrate layer (1) adopts glass or polymeric material, and the thickness of substrate layer (1) is 0.1-2mm.
3. a kind of large tracts of land organic solar energy cell structure according to claim 1; It is characterized in that; The material of said hole passive electrode layer (2) adopts indium tin oxide, fluorine tin-oxide or aluminium zinc oxide, and the thickness of hole passive electrode layer (2) is 20-400nm.
4. a kind of large tracts of land organic solar energy cell structure according to claim 1 is characterized in that, the material of said anode buffer layer (4) adopts metal oxide or organic substance, and the thickness of anode buffer layer (4) is 1-100nm.
5. a kind of large tracts of land organic solar energy cell structure according to claim 1; It is characterized in that the combination of one or more in said organic photoactive layer (5) employing metal phthalocyanine complex, polythiofuran derivative, polystyrene derivative or the fullerene derivate; Said organic photoactive layer (5) adopts individual layer, multilayer or mixed layer structure, and the thickness of organic photoactive layer (5) is 20-500nm.
6. a kind of large tracts of land organic solar energy cell structure according to claim 1 is characterized in that, said cathode buffer layer (6) adopts organic substance or metal oxide, and the thickness of cathode buffer layer (6) is 0.5-50nm.
7. a kind of large tracts of land organic solar energy cell structure according to claim 1 is characterized in that, said electronic collection electrode layer (7) adopts metal A l, metal Ca or Mg:Ag alloy; The thickness of electronic collection electrode layer (7) is 10-200nm.
8. based on the preparation method of the described a kind of large tracts of land organic solar energy cell structure of claim 1, it is characterized in that this method is realized by following steps:
Step 1, on substrate, adopt direct current magnetron sputtering process deposition hole passive electrode layer (2); Step 2, go up to adopt direct current magnetron sputtering process deposition layer of metal film, etching metal grill auxiliary electrode layer (3) on metallic film at the described hole of step 1 passive electrode layer (2); The thickness of metal grill auxiliary electrode layer (3) is 20-200nm;
Step 3, on the described metal grill auxiliary electrode layer of step 2 (3) deposition anode resilient coating (4), organic photoactive layer (5) and cathode buffer layer (6) successively;
Step 4, go up to adopt vacuum thermal evaporation process deposits electronic collection electrode layer (7) at the described cathode buffer layer of step 3 (6).
Step 3 described on metal grill auxiliary electrode layer (3) deposition anode resilient coating (4), organic photoactive layer (5) and cathode buffer layer (6) successively, deposition process is for adopting vacuum thermal evaporation technology or solution spin coating proceeding deposition.
9. the preparation method of a kind of large tracts of land organic solar energy cell structure according to claim 8 is characterized in that, the described metal grill auxiliary electrode layer of step 2 (3) line thickness is 0.1-2mm.
10. the preparation method of a kind of large tracts of land organic solar energy cell structure according to claim 8 is characterized in that, the lithographic method of the described metal grill auxiliary electrode layer of step 2 is: adopt the wet etching technique etching.
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| CN102881830A (en) * | 2012-09-28 | 2013-01-16 | 北京大学 | Organic solar cell and manufacturing method thereof |
| CN103466696A (en) * | 2013-08-20 | 2013-12-25 | 中南大学 | Preparation method and application of high dispersity TiO2 nanocrystalline |
| CN103606627A (en) * | 2013-12-06 | 2014-02-26 | 电子科技大学 | Organic solar cell with metal-mesh-nested heterogeneous junctions and preparation method for organic solar cell |
| CN105393376A (en) * | 2013-06-14 | 2016-03-09 | 株式会社Lg化学 | Organic photovoltaic cell and method for manufacturing same |
| CN106206955A (en) * | 2016-08-15 | 2016-12-07 | 华中科技大学 | A kind of flexible solar battery |
| CN108574049A (en) * | 2018-06-30 | 2018-09-25 | 中国科学院上海硅酸盐研究所 | A kind of perovskite solar cell module and preparation method thereof |
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| CN102881830A (en) * | 2012-09-28 | 2013-01-16 | 北京大学 | Organic solar cell and manufacturing method thereof |
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| CN103466696A (en) * | 2013-08-20 | 2013-12-25 | 中南大学 | Preparation method and application of high dispersity TiO2 nanocrystalline |
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| CN103606627B (en) * | 2013-12-06 | 2016-01-27 | 电子科技大学 | Organic solar batteries of the nested heterojunction of wire netting and preparation method thereof |
| CN103606627A (en) * | 2013-12-06 | 2014-02-26 | 电子科技大学 | Organic solar cell with metal-mesh-nested heterogeneous junctions and preparation method for organic solar cell |
| CN106206955A (en) * | 2016-08-15 | 2016-12-07 | 华中科技大学 | A kind of flexible solar battery |
| CN108574049A (en) * | 2018-06-30 | 2018-09-25 | 中国科学院上海硅酸盐研究所 | A kind of perovskite solar cell module and preparation method thereof |
| CN108666426A (en) * | 2018-06-30 | 2018-10-16 | 中国科学院上海硅酸盐研究所 | A kind of perovskite solar cell module and preparation method thereof |
| CN109494304A (en) * | 2018-11-20 | 2019-03-19 | 东南大学 | A kind of high height thoroughly of solar battery leads the preparation method of membrane electrode |
| CN111326659A (en) * | 2020-02-24 | 2020-06-23 | 杭州电子科技大学 | Metal transparent electrode and organic solar cell |
| CN111326659B (en) * | 2020-02-24 | 2023-08-15 | 杭州电子科技大学 | Metal transparent electrode and organic solar cell |
| CN113421977A (en) * | 2021-05-26 | 2021-09-21 | 华为技术有限公司 | Solar cell, preparation method thereof, intelligent glasses and electronic equipment |
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