Modification of silicon layers formed from silane-containing formulations

1. A process for preparing a silicon layer on a substrate, the silicon layer comprising silicon and a surface suboxide structure, the process comprising:

(I) applying a formulation comprising at least one silicon compound to the substrate, to obtain a coated substrate;

(II) irradiating, thermally treating, or irradiating and thermally treating the coated substrate to form a silicon layer;

(III) treating the silicon layer with at least one oxygen source selected from the group consisting of elemental oxygen, O 3 , carbon dioxide, and an oxygen-comprising compound, wherein the oxygen source is in pure form or a liquid or gaseous mixture; and

(IV) irradiating, thermally treating, or irradiating and thermally treating the oxygen treated coated substrate, to form the silicon layer comprising suboxide structures on a surface of the layer.

2. The process of claim 1 , wherein the treatment of the silicon layer with the at least one oxygen source (III) is effected by either:

i) contacting the silicon layer with at least one oxygen source selected from the group consisting of gaseous elemental oxygen, gaseous 0 3 , gaseous carbon dioxide, and the oxygen-comprising compound, which has been converted to a gaseous form; or

ii) applying to the silicon layer a liquid formulation comprising at least one oxygen source selected from the group consisting of dissolved elemental oxygen, dissolved O 3 , dissolved carbon dioxide, and the oxygen-comprising compound.

3. The process of claim 1 , further comprising:

repeating (I), (II), (III), and (IV), to form a further silicon layer comprising suboxide structures on the surface of the silicon layer.

4. The process of claim 1 , wherein the oxygen source is the oxygen-comprising compound, and the oxygen-comprising compound is at least one selected from the group consisting of H 2 O, an alcohol, a diol, a triol, an aldehyde, a ketone, a carboxylic acid, a carbonic ester, and a compound of formula (I)

R 1 R 2 SiR 3 R 4   (I)

wherein, in formula (I), at least one of R 1 to R 4 comprises a structure of —O—R, wherein R is H, an alkyl group, an aryl group, or an alkylaryl group.

5. The process of claim 1 , wherein the substrate is electrically conductive or comprises an electrically conductive surface.

6. The process of claim 1 , wherein the silicon compound of the formulation is at least one selected from the group consisting of:

a silicon-hydrogen compound of formula (a):

Si n H 2n+2   (a),

wherein n is 3 to 10:,

a silicon-hydrogen compound of formula (b):

Si n H 2n   (b),

wherein n is 4 to 8;

a silicon halide;

a silicon organyl;

an oligomeric silicon compound of formula (c):

Si n R 2n+2   (c),

wherein n 8 to 100, and each R is independently a hydrogen, a halogen, or an organyl; and

an oligomeric silicon compound of formula (d):

Si n R 2n   (d)

wherein n is 8 to 100, and each R is independently a hydrogen, a halogen, or an organyl.

7. The process of claim 1 , wherein the formulation is a liquid formulation comprising a solvent, and wherein a viscosity of the liquid formulation is from 1 to 2000 mPas.

8. The process of claim 1 , wherein the substrate is coated by: casting; knife-coating; casting and knife-coating; printing; spraying; rotary coating; dipping; meniscus coating; slit coating; slot-die coating; or curtain coating.

9. The process of claim 1 , wherein the coated substrate, the oxygen treated coated substrate, or both, is thermally treated at a temperature of from 200 to 1000° C.

10. A photovoltaic unit, produced by the process of claim 1 .

11. A coated substrate comprising a layer sequence, wherein the layer sequence is either:

substrate//i-Si(subox),

substrate//i-Si//i-Si(subox),

substrate//n-Si//i-Si(subox)//i-Si//i-Si(subox)//p-Si,

substrate//p-Si//i-Si(subox)//i-Si//i-Si(subox)//n-Si,

substrate//i-Si(subox)//n-Si//i-Si(subox)//i-Si//i-Si(subox)//p-Si//i-Si(subox); or

substrate//i-Si(subox)//p-Si//i-Si(subox)//i-Si//i-Si(subox)//n-Si//i-Si(subox),

substrate//n-Si//p-Si//p-Si(subox)//n-Si//i-Si//p-Si

substrate//p-Si//n-Si//n-Si(subox)//p-Si//i-Si//n-Si

substrate//n-Si//i-Si//p-Si//p-Si(subox)//n-Si//i-Si//p-Si

substrate//p-Si//i-Si//n-Si//n-Si(subox)//p-Si//i-Si//n-Si;

wherein i-Si(subox), p-Si(subox) and n-Si(subox) are an at least partly polymorphic layer comprising silicon and comprising suboxide structures on a surface thereof or throughout.

12. The coated substrate of claim 11 , wherein the substrate is electrically conductive or comprises an electrically conductive surface.

13. A process for producing an at least partly polymorphic layer comprising silicon and comprising suboxide structures on a surface thereof or throughout, the process comprising:

treating with at least one oxygen source selected from the group consisting of elemental oxygen, carbon dioxide, an oxygen-comprising compound, wherein the oxygen source is in pure form or a liquid or gaseous mixture.

14. A process for preparing a silicon layer on a substrate, the silicon layer comprising polymorphic silicon and suboxide structures throughout the layer, the process comprising:

(I′) coating the substrate with a formulation comprising at least one silicon compound and at least one oxygen source selected from the group consisting of elemental oxygen, O 3 , carbon dioxide, and an oxygen-comprising compound, wherein the oxygen source is in pure form or a liquid or gaseous mixture, and

(II′) irradiating, thermally treating, or irradiating and thermally treating the coated substrate, to form the at least partly polymorphic layer of silicon comprising suboxide structures throughout.

15. The process of claim 14 , further comprising: repeating (I′) and (II′), to form a further at least partly polymorphic silicon layer comprising suboxide structures throughout.

16. The process of claim 14 , wherein the oxygen source is the oxygen-comprising compound, and the oxygen-comprising compound is at least one selected from the group consisting of H 2 O, an alcohol, a diol, a triol, an aldehyde, a ketone, a carboxylic acid, a carbonic ester, and compound of formula (I):

R 1 R 2 SiR 3 R 4   (I),

wherein, in formula (I): at least one of R 1 to R 4 comprises a structure of —O—R, wherein R is H, an alkyl group, an aryl group or an alkylaryl group.

17. The process of claim 14 , wherein the substrate is electrically conductive or comprises an electrically conductive surface.

18. The process of claim 14 , wherein the silicon compound of the formulation is at least one in the group consisting of:

a silicon-hydrogen compound of formula (a):

Si n H 2n+2   (a),

wherein n is 3 to 10:,

a silicon-hydrogen compound of formula (b):

Si n H 2n   (b),

wherein n is 4 to 8;

a silicon halide;

a silicon organyl;

an oligomeric silicon compound of formula (c):

Si n R 2n+2   (c),

wherein n is 8 to 100, and each R is independently a hydrogen, a halogen, or an organyl; and

an oligomeric silicon compound of formula (d):

Si n R 2n   (d)

wherein n is 8 to 100, and each R is independently a hydrogen, a halogen, or an organyl.

19. The process of claim 14 , wherein the formulation is a liquid formulation comprising a solvent, and wherein a viscosity of the liquid formulation is from 1 to 2000 mPas.

20. The process of claim 14 , wherein the substrate is coated by: casting; knife-coating;, casting and knife-coating; printing; spraying; rotary coating; dipping; meniscus coating; slit coating; slot-die coating; or curtain coating.

21. The process of claim 14 , wherein the coated substrate is thermally treated at a temperature of from 200 to 1000° C.