IP Library Granted Patent US 9,391,287
Granted Patent B1
US 9,391,287 · App. 14/576,878 · Granted Jul 12, 2016

Photovoltaic perovskite material and method of fabrication

Inventors: Jinsong Huang (Lincoln, NE); Qingfeng Dong (Lincoln, NE); Rui Dong (Lincoln, NE); Yuchuan Sao (Lincoln, NE); Cheng Bi (Lincoln, NE); Qi Wang (Lincoln, NE); Zhengguo Xiao (Lincoln, NE)
Assignee: THE BOARD OF REGENTS OF THE UNIVERSITY OF NEBRASKA
H01L51/4213H01L51/442H01L51/005H01L51/0037
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 9,391,287
App. No.
14/576,878
Granted
Jul 12, 2016
Kind
B1
Abstract

A semiconductor device and a method for fabrication of the semiconductor device are described that include a perovskite layer formed using a solution process with lead iodine and methylammonium halide. In an implementation, a semiconductor device that employs example techniques in accordance with the present disclosure includes a cathode layer; an anode layer; and an active layer disposed between the cathode layer and the anode layer, where the active layer includes a perovskite layer including an interdiffused and annealed lead iodine (PbI 2 ) film and methylammonium halide (CH 3 NH 3 X) film. In implementations, a process for fabricating a continuous-perovskite semiconductor device that employs example techniques in accordance with the present disclosure includes spinning a PbI 2 layer onto an ITO-covered glass; spinning an MAI layer onto the PbI 2 layer; annealing the PbI 2 layer and the MAI layer; spinning a PCBM layer onto a resulting perovskite layer; and depositing an Al layer.

Claims (38)

1. A semiconductor device, comprising:

a cathode layer;

an anode layer; and

an active layer disposed between the cathode layer and the anode layer, where the active layer includes a perovskite layer including an interdiffused and annealed lead(H) iodide (PbI 2 ) film and methylammonium halide (CH 3 NH 3 X) film, wherein the perovskite layer includes a graded composition with increased Pb and I toward one of the cathode layer or anode layer, wherein X includes at least one of Cl, Br, or I.

2. The semiconductor device of claim 1 , wherein the perovskite layer includes organometal trihalide perovskite (CH 3 NH 3 PbI 2 X) where X includes at least one of Cl, Br, or I.

3. The semiconductor device of claim 1 , further comprising:

a first buffer layer disposed between the active layer and the cathode;

a carrier trapping layer disposed between the active layer and the first buffer layer; and

a second buffer layer disposed between the active layer and the anode, the first buffer layer having a higher electron conductivity than the second buffer layer, the second buffer layer having a higher hole conductivity than the first buffer layer.

4. The semiconductor device of claim 1 , wherein the active layer includes at least one of polyvinyl carbazole (PVK), poly(3-hexylthiophene) (P3HT), poly[4,8-bis-(2-ethyl-hexylthiophene-5-yl)-benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]-alt-[2-(2′-ethyl-hexanoyl)-thieno[3,4-b]thiophen-4,6-diyl (PBDTTT-CT), phthalocyanine complex, a porphyrin complex, a polythiophene (PT), a derivative of polythiophene, a polycarbazole, a derivative of polycarbazole, a poly(p-phenylene vinylene) (PPV), a derivative of poly(p-phenylene vinylene), a polyfluorene (PF), a derivative of poly fluorene, a cyclopentadithiophene-based polymer, a benzodithiophene (BDT)-based polymer, a polythiophene, a derivative of polythiophene, a polycarbazole, a derivative of poly carbazole, poly(3-octylthiophene) (P30T), poly(3-hexyloxythiophene) (P3DOT), poly(3-methylthiophene) (PMeT), poly(3-dodecylthiophene) (P3DDT), poly(3-dodecylthienylenevinylene) (PDDTV), poly(3,3 dialkylquarterthiophene) (PQT), poly-dioctyl-fluorene-co-bithiophene (F8T2), poly-(2,5,-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (PBTTT-C12), poly[2,7-(9,9′-dihexylfluorene)-alt-2,3-dimethyl-5,7-dithien-2-yl-2,1,3-benzothiadiazole] (PFDDTBT), poly{[2,7-(9,9-bis-(2-ethylhexyl)-fluorene)]alt-[5,5-(4,7-di-20-thienyl-2,1,3-benzothiadiazole)]} (BisEH-PFDTBT), poly{[2,7-(9,9-bis-(3,7-dimethyl-octyl)-fluorene)]-alt-[5,5-(4,7-di-20-thienyl-2,1,3-benzothiadiazole)]} (BisDMOPFDTBT), poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT), or a combination of at least two of the above materials.

5. The semiconductor device of claim 1 , wherein the cathode includes at least one of aluminum, calcium, magnesium, lithium, sodium, potassium, strontium, cesium, barium, iron, cobalt, nickel, copper, silver, zinc, tin, samarium, ytterbium, chromium, gold, graphene, an alkali metal fluoride, an alkaline-earth metal fluoride, an alkali metal chloride, an alkaline-earth metal chloride, an alkali metal oxide, an alkaline-earth metal oxide, a metal carbonate, a metal acetate, or a combination of at least two of the above materials.

6. The semiconductor device of claim 1 , wherein the anode includes at least one of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), antimony-tin mixed oxide (ATO), a conductive polymer, a network of metal nanowire, a network of carbon nanowire, nanotube, nanosheet, nanorod, carbon nanotube, silver nanowire, or graphene.

7. The semiconductor device of claim 1 , wherein the second buffer layer includes at least one of LiF, CsF, LiCoO 2 , CS 2 CO 3 , TiO x , TiO 2 nanorods (NRs), ZnO, ZnO nanorods (NRs), ZnO nanoparticles (NPs), ZnO, Al 2 O 3 , CaO, bathocuproine (BCP), copper phthalocyanine (CuPc), pentacene, pyronin B, [6,6]-phenyl C61-butyric acid methyl ester (PCBM), [6,6]-phenyl C61-butyric acid methyl ester (PC70BM), pentadecafluorooctyl phenyl-C60-butyrate (F-PCBM), C60, C60/LiF, ZnO NRs/PCBM, ZnO/cross-linked fullerene derivative (C-PCBSD), single walled carbon nanotubes (SWCNT), poly(ethylene glycol) (PEG), poly(dimethylsiloxaneblock-methyl methacrylate) (PDMS-b-PMMA), polar polyfluorene (PF-EP), polyfluorene bearing lateral amino groups (PFN), polyfluorene bearing quaternary ammonium groups in the side chains (WPF-oxy-F), polyfluorene bearing quaternary ammonium groups in the side chains (WPF-6-oxy-F), fluorene alternating and random copolymer bearing cationic groups in the alkyl side chains (PFNBr-DBTI5), fluorene alternating and random copolymer bearing cationic groups in the alkyl side chains (PFPNBr), or poly(ethylene oxide) (PEO).

8. The semiconductor device of claim 1 , wherein the active layer absorbs light having a wavelength in a first predetermined range.

9. The semiconductor device of claim 3 , wherein the carrier trapping layer includes at least one of zinc oxide (ZnO x ), titanium oxide (TiO x ), tin oxide (SnO x ), zinc sulfide (ZnS), cadmium sulfide (CdS), lead sulfides (PbS), iron sulfide (FeS), iron pyrite (FeS 2 ), cadmium selenide (CdSe), lead selenide (PbSe), cadmium telluride (CdTe), lead telluride (PbTe), Si, Ge, InAs InSb, Pb 1-x SnxTe, Hg 1-x Cd x Te, InAsSb, InNSb, InBiTe, or InTlSb.

10. The semiconductor device of claim 3 , wherein the carrier trapping layer includes at least one of an InAs/GaInSb super lattice, a HgTe/CdTe super lattice, graphene quantum dots, a carbon nanotube, or fullerene.

11. The semiconductor device of claim 3 , wherein the first buffer layer includes at least one of an organic material or a self-assembled monolayer (SAM).

12. The semiconductor device of claim 3 , wherein the first buffer layer includes at least one of poly(3,4-ethylenedioxithiophene) (PEDOT) doped with poly(styrene sulfonicacid) (PSS), 4,4′bis[(ptrichlorosilylpropylphenyl)phenylamino]biphenyl (TPD-Si 2 ), poly(3-hexyl-2,5-thienylene vinylene) (P3HTV) and C60, copper phthalocyanine (CuPc), poly[3,4-(1hydroxymethyl) ethylenedioxythiophene] (PHEDOT), n-dodecylbenzenesulfonic acid/hydrochloric acid-doped poly(aniline) nanotubes (a-PANIN)s, poly(styrenesulfonic acid)-graft-poly(aniline) (PSSA-g-PANI), poly[(9,9-dioctylfluorene)-co-N-(4-(1-methylpropyflphenyfldiphenylamine] (PFT), 4,4′bis[(p-trichlorosilylpropylphenyl)phenylamino]biphenyl (TSPP), 5,5′-bis[(p-trichlorosilylpropylphenyl)phenylamino]-2,20-bithiophene (TSPT), N-propyltriethoxysilane, 3,3,3-trifluoropropyltrichlorosilane or 3-aminopropyltriethoxysilane V 2 O 5 , VO x , MoO 3 , WO 3 , ReO 3 , NiO x , AgO x /PEDOT:PSS, Cu 2 O, CuSCN/P3HT, or Au nanoparticles.

13. The semiconductor device of claim 3 , wherein the second buffer layer includes at least one of an alkali metal compound, a metal oxide, an organic material, or self-assembled mono layers (SAMs).

14. The semiconductor device of claim 3 , wherein the carrier trapping layer includes at least one of a fullerene, a derivative of fullerene, a perylene derivative, a 2,7-dicyclohexyl benzo, phenanthroline derivative, a 1,4-diketo-3,6-dithienylpyrrolo[3,4-c]pyrrole (DPP) derivative, a tetracyanoquinodimethane (TCNQ) derivative, indene-C60 bisadduct ([60]ICBA), indene-C70 bisadduct ([70]ICBA), a poly(p-pyridyl vinylene) (PPyV) derivative, a 9,9′-bifluorenylidene (99BF) derivative, a benzothiadiazole (BT) derivative, [6,6]-phenyl C61-butyric acid methyl ester (PCBM), [6,6]-phenyl C61-butyric acid methyl ester (PC70BM), [6,6]-(4-fluoro-phenyl)C61-butyric acid methyl ester (FPCBM), carbon 60 (C60), carbon 70 (C70), carbon nanotube (CNT), a carbon onion, or a combination of two or more of the above materials.

15. The semiconductor device of claim 8 , wherein the anode is at least one of transparent or partially transparent to light having a wavelength in a second predetermined range, the second predetermined range overlapping the first predetermined range in a third predetermined range.

16. A process for fabricating a continuous-perovskite photodetector device, comprising:

forming a pre-mixed perovskite layer pre-cursor on a cathode layer, the pre-cursor including lead iodide (PbI 2 ) and a methylammonium halide (CH 3 NH 3 X), wherein X includes at least one of Cl, Br or I;

annealing the pre-mixed perovskite layer pre-cursor to form a perovskite layer; and

forming an anode layer on the perovskite layer,

wherein the perovskite layer includes a graded composition with increased Pb and I toward one of the cathode layer or anode layer.

17. The process of claim 16 , wherein the pre-mixed perovskite layer pre-cursor includes a precursor molar ratio of lead iodine (PbI 2 ) to methylammonium halide of about 0.5 to about 0.9.

18. A process for fabricating a continuous-perovskite photodetector device, comprising:

forming a lead iodide (PbI 2 ) layer onto a cathode layer covered glass;

forming a methylammonium halide (CH 3 NH 3 X) layer onto the lead iodine layer, wherein X includes at least one of Cl, Br, or I;

annealing the lead iodine layer and the methylammonium halide layer to form a perovskite layer; and

forming an anode layer on the perovskite layer.

19. The process of claim 18 , wherein forming an anode layer includes forming an aluminum layer.

20. The process of claim 18 , wherein forming a lead iodine (PbI 2 ) layer onto a cathode layer covered glass includes forming a lead iodine (PbI 2 ) layer onto an Indium-Tin-oxide covered glass.

21. The process of claim 18 , further comprising forming a PCBM layer onto the perovskite layer.

22. The process of claim 18 , wherein annealing the lead iodine layer and the methylammonium halide layer to form a perovskite layer includes:

annealing the lead iodine layer and the methylammonium halide layer at a temperature of about 80° C. to about 120° C. for about 30 to about 180 minutes to form the perovskite layer.

23. The process of claim 18 , wherein the perovskite layer includes a graded composition with increased Pb and I toward one of the cathode layer or anode layer.

Assignments (3)
CONFIRMATORY LICENSE Recorded Sep 3, 2019
From: NEBRASKA, UNIVERSITY OF
To: NAVY, SECRETARY OF THE UNITED STATES OF AMERICA
Reel/Frame 050275/0395 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 23, 2015
From: HUANG, JINSONG; DONG, QINGFENG; DONG, RUI; SAO, YUCHUAN; BI, CHENG; WANG, QI; XIAO, ZHENGGUO
To: THE BOARD OF REGENTS OF THE UNIVERSITY OF NEBRASKA
Reel/Frame 034799/0807 →
CONFIRMATORY LICENSE Recorded Jan 5, 2015
From: UNIVERSITY OF NEBRASKA LINCOLN
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 034724/0808 →
Continuity (1)
Provisional Application 61918330 · Dec 19, 2013