PHOTOVOLTAIC DEVICES AND METHODS OF MAKING

1 . A photovoltaic device comprising:

an absorber layer on a substrate stack, the absorber layer comprising cadmium;

a p-type contact layer formed over a back interface at a second surface of the absorber layer; and

an improved carrier extraction (ICE) layer between the absorber layer and the p-type contact layer, wherein:

the ICE layer is in contact with the back interface of the absorber layer,

the ICE layer comprises sulfur in a deprotonated thiol compound, and

a surface workfunction of the ICE layer on the absorber layer is tunable by selection of thiol compound over a 600 meV range as measured by Kelvin Probe measurements of surface workfunction.

2 . (canceled)

3 . The device of claim 1 , wherein the absorber layer comprises tellurium and wherein a ratio of Cd to Te in a surface region of the absorber layer is within a range from 1:1 to 4:1.

4 . The device of claim 1 , wherein the thiol compound has a molecular dipole of strength greater than 0.5 debye.

5 . The device of claim 1 , wherein the surface workfunction of the ICE layer has a value magnitude within a range of 4.55 eV to 5.15 eV, measured after ICE layer deposition, or 4.6 eV to 5.0 eV, measured after HTM layer deposition.

6 . The device of claim 1 , wherein the thiol compound comprises at least one of: isothiourea, cysteamine, also known as 2-aminoethanethiol (AET); 4-fluorothiophenol (4-FTP); 4-aminothiophenol (4-ATP); 1,2-ethanedithiol, also known as ethylene mercaptan (EDT); L-cysteine, also known as (R)-2-amino-3-mercaptopropionic acid (L-Cys); thioglycolic acid, also known as mercaptoacetic acid (TGA); 1-octanethiol (OT); 4-fluorobenzyl mercaptan, also known as (4-fluorophenyl) methanethiol;

3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanethiol (TDF-OT); or 4-trifluoromethylbenzyl mercaptan (4-TFMBM).

7 . The device of claim 1 , wherein the thiol compound comprises at least one of: TDF-OT, 4-FTP, OT, AET, or 4-FBM.

8 . The device of claim 1 , wherein the p-type contact layer comprises at least one of: PTAA, poly-TPD, TFB, PF8-TAA, PIF8-TAA, NiOx, or P3HT.

9 . The device of claim 1 , wherein surface workfunction with the presence of an ICE layer is increased by up to 450 meV as compared to a surface without an ICE layer, or decreased by up to 150 meV with the presence of an ICE layer as compared to a surface without an ICE layer.

10 . The device of claim 1 , wherein:

the absorber layer comprises a type II-VI semiconductor, wherein the type II material includes cadmium (Cd) and the type VI material includes tellurium (Te);

the absorber layer is doped with at least one dopant selected from phosphorus, arsenic, antimony, or bismuth;

the ICE layer is directly adjacent to a second surface of the absorber layer at a passivated surface region, wherein a ratio of Cd to Te in the passivated surface region is greater than or equal to 1:1;

the p-type contact layer is directly adjacent to a second surface of the ICE layer;

the p-type contact layer comprises at least one of PTAA, P3HT, poly-TPD, TFB, TTF-1, PF8-TAA, PIF8-TAA, SGT-407, PCDTBT, SpiroOMeTAD, anthracene-based HTM, polythiophene, semiconducting polymer, NiO, CuSCN, or CuI; and

the device comprises a conductive layer on the p-type contact layer.

11 - 13 . (canceled)

14 . The device of claim 1 , wherein the ICE layer has a thickness in a range from 0.2 nm to 5.0 nm.

15 . A method of making a photovoltaic device comprising:

providing an absorber layer stack having an absorber layer comprising cadmium (Cd);

passivating a surface region of the absorber layer to form a passivated surface at a second surface of the absorber layer;

forming an improved carrier extraction (ICE) layer over the passivated surface, wherein:

the ICE layer contacts the second surface of the absorber layer, and

the ICE layer comprises sulfur in a deprotonated thiol compound; and

forming a p-type contact layer over the ICE layer.

16 . The method of claim 15 , wherein a surface workfunction of the ICE layer on the absorber layer is tunable by selection of thiol compound over a 600 meV range as measured by Kelvin Probe measurements of surface workfunction.

17 . The method of claim 15 , wherein the passivating step comprises contacting the second surface of the absorber layer with an alkaline passivation agent.

18 . The method of claim 15 , wherein the absorber layer comprises tellurium and wherein a ratio of Cd to Te in the surface region of the absorber layer is within a range from 1:1 to 4:1.

19 . The method of claim 15 , wherein the ICE layer comprises sulfur, and wherein the sulfur forms a complex with Cd at the passivated surface, and whereby the ICE layer produces a photoluminescence intensity enhancement of 2-10 times the photoluminescence intensity as compared to a comparable device lacking an ICE layer.

20 . The method of claim 15 , wherein the ICE layer comprises a compound selected from the group consisting of: isothiourea, AET; 4-FTP; 4-ATP; EDT; L-Cys; TGA; OT; 4-FBM; TDF-OT; or 4-TFMBM.

21 . (canceled)

22 . The method of claim 15 , wherein the passivating step comprises: contacting the surface of the absorber layer with an alkaline passivation agent, and wherein the alkaline passivation agent comprises at least one of: sodium hydroxide (NaOH), potassium hydroxide (KOH), or tetramethylammonium hydroxide (TMAH).

23 . (canceled)

24 . The method of claim 15 , wherein providing the absorber layer stack comprises forming the absorber layer over a substrate stack, wherein the absorber layer comprises a type II-VI semiconductor, and wherein forming the absorber layer further comprises doping, passivating; and removing oxides from the type II-VI semiconductor prior to depositing the ICE layer.

25 . The method of claim 15 , wherein the ICE layer comprises a monolayer of thiol ligands with dipole moments aligned relative to the second surface of the absorber layer.

26 . The method of claim 15 , wherein the ICE layer comprises a thiophenol or alkanethiol compound.

27 - 77 . (canceled)