Perovskite surface defect passivation using zwitterionic amino acids

Abstract

Semiconductor devices including a cathode layer, an anode layer, an active layer disposed between the cathode layer and the anode layer, wherein the active layer includes a perovskite layer, and a passivation layer disposed directly on a surface of the active layer between the cathode layer and the active layer, the passivation layer including a zwitterionic amino acid, such as valine or phenylalanine or other amino acid that passivates both cationic and anionic defects in the surface of the active layer.

1 . A semiconductor device, comprising:
 a cathode layer;   an anode layer;   an active layer disposed between the cathode layer and the anode layer, where the active layer includes a perovskite layer; and   a passivation layer disposed directly on a surface of the active layer between the cathode layer and the active layer, the passivation layer comprising a layer of material that passivates both cationic and anionic defects in the surface of the active layer, wherein the layer of material comprises a zwitterionic amino acid.   
     
     
         2 . The semiconductor device of  claim 1 , wherein the perovskite layer includes organometal trihalide perovskite having the formula ABX 3 , or A 2 BX 4 , wherein A is methylammonium (CH 3 NH 3   + ), formamidinium (H 2 NCHNH 2   + ), or an alkali-metal ion , B is a metal cation, and X is a halide anion, thiocyanate (SCN-) or a mixture thereof. 
     
     
         3 . The semiconductor device of  claim 1 , further comprising:
 a first carrier transport layer disposed between the passivation layer and the cathode; and   a second carrier transport layer disposed between the active layer and the anode, the first carrier transport layer having a higher electron conductivity than the second carrier transport layer, the second carrier transport layer having a higher hole conductivity than the first carrier transport layer.   
     
     
         4 . The semiconductor device of  claim 3 , wherein:
 the first carrier transport layer comprises at least one C60, a fullerene, a fullerene-derivative, LiF, CsF, LiCoO2, CS2CO3, TiOx, TiO2 nanorods (NRs), ZnO, ZnO nanorods (NRs), ZnO nanoparticles (NPs), ZnO, Al2O3, CaO, bathocuproine (BCP), copper phthalocyanine (CuPc), pentacene, pyronin B, 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), Polyethylenimine (PEI), 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).; and   the second carrier transport layer comprises at least one poly(3,4-ethylenedioxithiophene) (PEDOT) doped with poly(styrene sulfonicacid) (PSS), 4,4′bis[(ptrichlorosilylpropylphenyl)phenylamino]biphenyl (TPD-Si2), 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-methylpropyl)phenyl)diphenylamine] (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-aminopropyltriethoxysilanePoly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), V2O5, VOx, MoO3, WO3, ReO3, NiOx, AgOx/PEDOT:PSS, Cu2O, CuSCN/P3HT, or Au nanoparticles.   
     
     
         5 . The semiconductor device of  claim 1 , further comprising a fullerene layer disposed on the passivation layer between the passivation layer and the first carrier transport layer. 
     
     
         6 . The semiconductor device of  claim 5 , wherein the fullerene layer comprises a layer of C 60  having a thickness of between about 1 nm and about 100 nm. 
     
     
         7 . The semiconductor device of  claim 1 , wherein the anode layer 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. 
     
     
         8 . The semiconductor device of  claim 1 , wherein the cathode layer includes at least one of copper, aluminum, calcium, magnesium, lithium, sodium, potassium, strontium, cesium, barium, iron, cobalt, nickel, 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. 
     
     
         9 . The semiconductor device of  claim 1 , wherein the passivation layer has a thickness of between about 1 nm and about 30 nm. 
     
     
         10 . The semiconductor device of  claim 1 , wherein the zwitterionic amino acid comprises one of valine or phenylalanine. 
     
     
         11 . A semiconductor device, comprising:
 a cathode layer;   an anode layer;   an active layer disposed between the cathode layer and the anode layer, where the active layer includes an organometal trihalide perovskite having the formula ABX 3 , or A 2 BX 4 , wherein A is methylammonium (CH 3 NH 3   + ), an alkali metal ion or formamidinium (H 2 NCHNH 2   + ), B is a metal cation, and X is a halide anion, thiocyanate (SCN-) or a mixture thereof;   a passivation layer disposed directly on a surface of the active layer between the cathode layer and the active layer, the passivation layer comprising a layer of material that passivates both cationic and anionic defects in the surface of the active layer, wherein the layer of material comprises a zwitterionic amino acid;   an electron extraction layer disposed directly on the passivation layer between the passivation layer and the cathode layer, the electron extraction layer comprising a layer of C 60 ;   a first carrier transport layer comprising bathocuproine (BCP) and disposed between the electron extraction layer and the cathode; and   a second carrier transport layer comprising Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) and disposed between the active layer and the anode.   
     
     
         12 . The semiconductor device of  claim 11 , wherein the anode layer includes indium tin oxide (ITO) and wherein the cathode layer includes copper. 
     
     
         13 . The semiconductor device of  claim 11 , wherein the layer of C 60  has a thickness of between about 1 nm and about 100 nm. 
     
     
         14 . The semiconductor device of  claim 11 , wherein the active layer has a thickness of between about 1 nm and about 10 μm. 
     
     
         15 . The semiconductor device of  claim 11 , wherein the passivation layer has a thickness of between about 1 nm and about 30 nm. 
     
     
         16 . The semiconductor device of  claim 11 , wherein the zwitterionic amino acid comprises one of valine or phenylalanine. 
     
     
         17 . A method of making a semiconductor device, the process comprising:
 providing an active layer, where the active layer includes a perovskite material; and   applying a passivation layer directly on a surface of the active layer, the passivation layer comprising a first material that passivates both cationic and anionic defects in the surface of the active layer, wherein the first material comprises a zwitterionic amino acid.   
     
     
         18 . The method of  claim 17 , further comprising forming a cathode layer on the passivation layer. 
     
     
         19 . The method of  claim 18 , further comprising forming an anode layer on a side of the active layer so that the active layer is disposed between the cathode layer and the anode layer. 
     
     
         20 . The method of  claim 19 , further comprising
 forming a first carrier transport layer disposed between the passivation layer and the cathode layer; and   forming a second carrier transport layer disposed between the active layer and the anode layer, the first carrier transport layer having a higher electron conductivity than the second carrier transport layer, the second carrier transport layer having a higher hole conductivity than the first carrier transport layer.   
     
     
         21 . The method of  claim 17 , wherein the perovskite material includes organometal trihalide perovskite having the formula ABX 3 , or A 2 BX 4 , wherein A is methylammonium (CH 3 NH 3   + ), formamidinium (H 2 NCHNH 2   + ), or an alkali-metal ion , B is a metal cation, and X is a halide anion, thiocyanate (SCN-) or a mixture thereof. 
     
     
         22 . The method of  claim 17 , wherein the zwitterionic amino acid comprises one of valine or phenylalanine.