ORGANOMODIFIED METAL OXIDE OR METALLOID OXIDE POLYMER FILM

Abstract

The present invention relates to a process for preparing a thin film on a substrate comprising the steps of preparing two precursor compositions comprising metalloid compounds and combining them thereafter whereby one precursor composition is hydrolyzed prior to combination. The present invention is further related to a multilayer structure and an article comprising the thin film obtainable by the process, a composition comprising the precursor compositions, a kit-of-parts comprising the precursor compositions obtainable by the use of the composition and the kit-of-parts for preparing a thin film on a substrate.

Claims

1. A process for preparing a thin film on a substrate, the process comprising: a) preparing a first precursor composition (FPC) in a first vessel, wherein a) comprises: a1) providing one or more metal or metalloid compound(s) according to the following formula (I)
M.sup.1(OR.sup.1).sub.nR.sup.2.sub.m(I) wherein M.sup.1 is a metal or metalloid with a valence each R.sup.1 is independently a C.sub.1 to C.sub.10 organyl or organoheteryl group, each R.sup.2 is independently a C.sub.1 to C.sub.20 organyl or organoheteryl group, n is 1 to z, m is z1 to 0, and n+m is z; and a2) at least partially hydrolyzing the M.sup.1(OR.sup.1)-moieties and polymerizing the one or more metal or metalloid compound(s) according to formula (I) by b) preparing a second precursor composition (SPC) in a second vessel, wherein b) comprises: b1a) providing a metal or metalloid compound according to the following formula (II)
M.sup.2(OR.sup.3).sub.o(II) wherein M.sup.2 is a metal or metalloid with a valence y, wherein M.sup.1 and M.sup.2 are based on different elements of the periodic table, each R.sup.3 is independently a C.sub.1 to C.sub.10 organyl or organoheteryl group, and o is y; and b2a) optionally reacting the metal or metalloid compound according to formula (II) with a ligand (L) different from (OR.sup.3); or b1b) directly providing a reaction product of b2a); c) mixing the FPC with the SPC; c1) optionally reacting a product of c) with Si(R.sup.23).sub.3X or Si(R.sup.23).sub.2X.sub.2, wherein R.sup.23 is a C.sub.1-C.sub.3 alkyl group, and X represents Cl or OR.sup.24, wherein R.sup.24 is a C.sub.1-C.sub.3 alkyl group; d) forming a thin layer on the substrate; e) optionally partially or completely removing solvent, if present, after d); and f) curing an intermediate product obtained in e), if present, or d), if e) is not present, wherein, optionally a (meth)acrylate ester (ME) is added during a), during b), and/or during c) or after c) before d) is effected.

2. The process of claim 1, wherein, in c), a molar ratio between M.sup.1 and M.sup.2 is from 1.0:10 to 10:1.0.

3. The process of claim 1, wherein M.sup.1 and/or M.sup.2 is/are independently Si, Ge, Sb, Ti, Zr, Al, Sn, W, Se, Cr, Ag or Ni.

4. The process of claim 1, wherein, during c), an additive is added, wherein optionally the additive is selected from the group consisting of a surfactant, a levelling agent, a processing aid, an antistatic agent, an antioxidant, a water scavenger, an oxygen scavenger, a catalyst, a scatter particle, a photoinitiator and mixtures thereof.

5. The process of claim 1, wherein a maximum temperature during d) to f) is below 450 C.

6. The process of claim 1, further comprising, after c); c2) adding a solvent (S) to the mixture obtained in c).

7. The process of claim 1, wherein a solids content prior to d) is not more than 75 wt. %.

8. The process of claim 1, wherein a solids content prior to d) is at least 90 wt %.

9. The process of claim 1, wherein f) is effected by thermal and/or radiation curing.

10. A multi-layer structure comprising a layer consisting of a thin film prepared by the process of claim 1.

11. The multi-layer structure of claim 10, wherein one surface of the layer is in direct contact with one surface of the substrate and/or another layer.

12. An article comprising a thin film obtainable by the process of claim 1.

13. The article of claim 12, which is selected from the group consisting of: Optical and electrical coatings; High-k dielectrics; Light out-coupling/extraction layers; Etch and CMP stop layers; OLED protective/sealing/encapsulation coatings; Organic solar cells; and Optical thin film filters.

14. A composition comprising a first precursor composition (FPC) and a second precursor composition (SPC), the FPC being one or more polymerized metal or metalloid compound(s) according to the following formula (I)
M.sup.1(OR.sup.1).sub.nR.sup.2.sub.m(I) wherein M.sup.1 is a metal or metalloid with a valence z, each R.sup.1 is independently a C.sub.1 to C.sub.10 organyl or organoheteryl group, each R.sup.2 is independently a C.sub.1 to C.sub.20 organyl or organoheteryl group, n is 1 to z1. m is 1 to z1, and n+m is z, whereby wherein the polymerization is effected by at least partially hydrolyzing the M.sup.1(OR.sup.1)-moieties; and the SPC being obtainable by: b1a) providing a metal or metalloid compound according to the following formula (II)
M.sup.2(OR.sup.3).sub.o(II) wherein M.sup.2 is a metal or metalloid with a valence y, wherein M.sup.1 and M.sup.2 are based on different elements of the periodic table, each R.sup.3 is independently a C.sub.1 to C.sub.10 organyl or organoheteryl group, and o is y; and b2a) optionally reacting the metal or metalloid compound according to formula (II) with a ligand (L) different from (OR.sup.3); or b1b) directly providing a reaction product of b2a).

15. A kit-of-parts comprising a first precursor composition (FPC) in a first vessel and a second precursor composition (SPC) in a second vessel, the FPC being one or more polymerized metal or metalloid compound(s) according to the following formula (I)
M.sup.1(OR.sup.1).sub.nR.sup.2.sub.m(I) wherein M.sup.1 is a metal or metalloid with a valence z, each R.sup.1 is independently a C.sub.1 to C.sub.10 organyl or organoheteryl group, each R.sup.2 is independently a C.sub.1 to C.sub.20 organyl or organoheteryl group, n is 1 to z1, m is 1 to z1, and n+m is z, wherein the polymerization is effected by at least partially hydrolyzing the M.sup.1(OR.sup.1)-moieties; and the SPC being obtainable by b1a) providing a metal or metalloid compound according to the following formula (II)
M.sup.2(OR.sup.3).sub.o(II) wherein M.sup.2 is a metal or metalloid with a valence y, wherein M.sup.1 and M.sup.2 are based on different elements of the periodic table; each R.sup.3 is independently a C.sub.1 to C.sub.10 organyl or organoheteryl group, and o is y, and b2a) optionally reacting the metal or metalloid compound according to formula (II) with a ligand (L) different from (OR.sup.3); or b1b) directly providing a reaction product of b2a).

16. A method for preparing a thin film on a substrate and/or Optical and electrical coatings; High-k dielectrics; Light out-coupling/extraction layers; Etch and CMP stop layers; OLED protective/sealing/encapsulation coatings; Organic solar cells; or Optical thin film filters, the method comprising obtaining the composition of claim 14.

Description

[0326] FIG. 1 shows a simplified cross-section of bottom emission OLED device

[0327] FIG. 2 shows a simplified cross-section of a top emission OLED device

[0328] FIG. 3 shows a simplified cross-section of a top emission OLED device with thin film encapsulation layers

[0329] FIG. 4 shows the transmission graph of the film obtained in application example 19, (spectrum includes glass substrate).

[0330] FIG. 5 shows the transmission graph of the film obtained in application example 24, (glass substrate subtracted).

[0331] FIG. 6 shows the weight loss, determined by Thermogravimetric analysis (TGA) of application example 24

EXPERIMENTAL PART

Measuring Methods

[0332] Molecular weight of the polymer obtained after step a2)

[0333] The tool used the measure molecular weight is WATERS GPC (gel permeation chromatography): waters 1515 Isocratic HPLC pump, waters 2414 refractive index detector.

[0334] Polystyrene standards are used as calibration standards for the measurement. The actual samples for the measurements are prepared as 4m-% samples using THF as eluent solution.

Solids Content

[0335] The tool used to determine the molecular weight is Mettler Toledo HB43 Halogen dryer/balance.

[0336] Sample is weighted on aluminum dish/cup and measurement is performed using about 1 gram of material.

Shelf Life Determination

[0337] See application examples 24 and 24C for actual measurement data. Material shelf life is determined by following material process/application result stability/repeatability as cured film. The values monitored from cured film are film thickness and film refractive index. The film thickness and refractive index are characterized by using Ellipsometer (UVISEL-VASE Horiba Jobin-Yvon). Measurements are performed using Gorilla Glass 4 or silicon wafer (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: <1-0-0>, Resistivity: 1-30 ohm.Math.cm, Thickness: 675+/25 m, TTV: <5 m, Particle: <20@0.2 m, Front Surface: Polished, Back Surface: Etched, Flat:1 SEMI Standard) as substrates. Material film depositions are done by using spin coating, pre-cured using hot-plate, UV-exposure performed by broadband UV source and final bake performed in convection oven. Optionally materials can be UV-cured only or thermal cured only.

Viscosity

[0338] Tool manufacturer: Grabner Instruments Viscometer MINIVIS-II. Measurement method Falling ball viscosity measurement. Samples are measured at 20 C. by using steel ball with 3.175 mm diameter.

Transmission

[0339] Konica Minolta spectrophotometer CM-3700A (SpectraMagic NX software). The preparation of the specimen is described in the respective example.

Color and Haze Measurement

[0340] L*(D65), a*(D65) and b*(D65) and Haze were determined by using Konica Minolta spectrophotometer CM-3700A (Spectra Magic NX software). Measurements are performed using Gorilla Glass 4 as substrates. Material film depositions are done by using spin coating, pre-cured using hot-plate, UV-exposure performed by broadband UV source and final bake performed in convection oven. Optionally materials can be UV-cured only or thermal cured only. Also optionally the materials are ink-jet deposited on glass.

Refractive Index

[0341] The film refractive index is characterized by using Ellipsometer (UVISEL-VASE Horiba Jobin-Yvon). Measurements are performed using Gorilla Glass 4 or silicon wafer (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: <1-0-0>, Resistivity: 1-30 ohm.Math.cm, Thickness: 675+/25 m, TTV: <5 m, Particle: <20@0.2 m, Front Surface: Polished, Back Surface: Etched, Flat:1 SEMI Standard) as substrates. Material film depositions are done by using spin coating, pre-cured using hot-plate, UV-exposure performed by broadband UV source and final bake performed in convection oven. Optionally materials can be UV-cured only or thermal cured only. Also optionally the materials are ink-jet deposited on glass.

Film Thickness

[0342] The film thickness is measured by using Ellipsometer (UVISEL-VASE Horiba Jobin-Yvon). Measurements are performed using Gorilla Glass 4 or silicon wafer (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: <1-0-0>, Resistivity: 1-30 ohm.Math.cm, Thickness: 675+/25 m, TTV: <5 m, Particle: <20@0.2 m, Front Surface: Polished, Back Surface: Etched, Flat:1 SEMI Standard) as substrates. Material film depositions are done by using spin coating, pre-cured using hot-plate, UV-exposure performed by broadband UV source and final bake performed in convection oven. Optionally materials can be UV-cured only or thermal cured only. Also optionally the materials are ink-jet deposited on glass.

Thermogravimetric Analysis (TGA)

[0343] A sample of 2.0 mg weight was set in TGA/DTA Simultaneous Measuring Instrument DTG-60A, Shimadzu Japan, and heated up to 160 C., 230 C. and 250 C. continuously under Nitrogen flow atmosphere. The heating rate was 10 C./min and the temperature of 160 C. was held for 60 min, the temperature of 230 C. was held for 60 min and the temperature of 250 C. was held for 30 min.

EXPERIMENTAL RESULTS

Used Substances

[0344] MIRAMER M1142, o-phenylphenolethyleneoxide acrylate, CAS-no. 72009-86-0, MW =268 g/mol supplied by Miwon

[0345] MIRAMER M244, Bisphenol A (ethylene oxide).sub.3 diacrylate, CAS-no. 64401-02-1, MW=468 g/mol, supplied by Miwon

Inventive Example 1

[0346] 2.34 g of methacryloxypropylmethyldimethoxysilane, 0.5 g of water, 8 g of propyleneglycolmonomethylether and 0.2 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 16 g of propyleneglycolmonomethylether was added to the reaction mixture. 5.2 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely (5 min) at 80 C. (Gradual and slow addition is important. Otherwise, TiO2 particle generate). The mixture was stirred for 3 hours at 80 C., giving a transparent solution. The solids content (SC) of the obtained solution was 14 wt. %.

Inventive Example 2

[0347] The procedure of inventive example 1 was repeated except that 8.4 g of tetraisopropylorthotitanate was used, resulting in a transparent solution with an SC of 15 wt.%.

Inventive Example 3

[0348] The procedure of inventive example 2 was repeated except that instead of trimethylamine, 0.2 g of 2,6,10-trimethyl-2,6,10-triazaundecane was used, resulting in a transparent solution with an SC of 15 wt. %.

Inventive Example 4

[0349] The procedure of inventive example 1 was repeated except that 5.2 g of 3-glycidoxypropylmethyldimethoxysilane instead of methacryloxypropylmethyldimethoxysilane was used, resulting in a transparent solution with an SC of 14 wt. %.

Inventive Example 5

[0350] The procedure of inventive example 4 was repeated except that 11 g of 3-glycidoxypropylmethyldimethoxysilane was used, resulting in a transparent solution with an SC of 20 wt. %.

Inventive Example 6

[0351] 4.68 g of methacryloxypropylmethyldimethoxysilane, 1.0 g of water, 16 g of propyleneglycolmonomethylether and 0.4 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 32 g of propyleneglycolmonomethylether was added to the reaction mixture. 16.8 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely (4 min) at 80 C. The mixture was stirred for 3 hours at 130 C. and further stirred for 4 hours at 130 C. with distillation, resulting in a transparent solution with an SC of 17 wt. %.

Inventive Example 7

[0352] 4.68 g of glycidoxypropylmethyldimethoxysilane, 1.0 g of water, 16 g of propyleneglycolmonomethylether and 0.4 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 32 g of propyleneglycolmonomethylether was added to the reaction mixture. 22 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely (8 min) at 80 C. The mixture was stirred for 3 hours at 130C and further stirred for 4 hours at 130 C. with distillation, resulting in a transparent solution with an SC of 26 wt. %.

Inventive Example 8

[0353] 9.36 g of glycidoxypropylmethyldimethoxysilane, 2 g of water, 32 g of propyleneglycolmonomethylether and 0.8 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 64 g of propyleneglycolmonomethylether was added to the reaction mixture. 44 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely (18 min) at 80 C. The mixture was stirred for 3 hours at 80 C. Thereafter, the generated alcohol was removed by evaporation under reduced pressure, resulting in a transparent solution with an SC of 31 wt. %.

Inventive Example 9

[0354] The procedure of inventive example 1 was repeated except that 2.34 g of mercaptpropyl methyldimethoxysilane was used instead of methacryloxypropylmethyldimethoxysilane, resulting in a transparent solution with an SC of 17 wt. %.

Inventive Example 10

[0355] The procedure of inventive example 9 was repeated except that 8.4 g tetraisopropylorthotitanate was used, resulting in a transparent solution with an SC of 16 wt. %.

Inventive Example 11

[0356] 9.36 g of glycidoxypropylmethyldimethoxysilane, 2 g of water, 32g of propyleneglycolmonomethylether and 0.8 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 64 g of propyleneglycolmonomethylether was added to the reaction mixture. 59.6 g of titanium tetra n-butoxide was added to the reaction mixture drop-wisely (9 min) at 80 C. The mixture was stirred for 3 hours at 100 C., resulting in a transparent solution with an SC of 19 wt. %.

Inventive Example 12

[0357] The procedure of inventive example 5 was repeated whereby to 30 g of the resulting transparent solution 6 g of ethylacetoacetate was added and the resulting mixture was stirred for 24 h at 25 C., resulting in a transparent solution with an SC of 17 wt. %.

Inventive Example 13

[0358] The procedure of inventive example 5 was repeated whereby to 30 g of the resulting transparent solution 12 g of ethylacetoacetate was added and the resulting mixture was stirred for 48 h at 25 C., resulting in a transparent solution with an SC of 13 wt. %.

Inventive Example 14

[0359] 3.12 g of glycidoxypropylmethyldimethoxysilane, 9 g of dimethyldiethoxysilane, 2 g of water, 32 g of propyleneglycolmonomethylether and 0.8 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 64 g of propyleneglycolmonomethylether was added to the reaction mixture. 44 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely (7 min) at 80 C. The mixture was stirred for 3 hours at 100 C., resulting in a transparent solution with an SC of 16 wt. %.

Inventive Example 15

[0360] The procedure of inventive example 11 was repeated whereby to 20 g of the resulting transparent solution 4 g of ethylacetoacetate and 16 g propyleneglycolmonomethylether were added and the resulting mixture was stirred for 72 h at 25 C., resulting in a transparent solution with an SC of 10 wt. %.

Inventive Example 16

[0361] 2.11 g of methacryloylpropyltrimethoxysilane, 0.23 g of glycidoxypropylmethyldimethoxysilane, 0.5 g of water, 8 g of propyleneglycolmonomethylether and 0.2 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 16 g of propyleneglycolmonomethylether was added to the reaction mixture. 8.4 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely at 80 C. The mixture was stirred for 6 hours at 80 C., resulting in a transparent solution with an SC of 17 wt. %.

Inventive Example 17

[0362] 2.34 g of glycidoxypropyltrimethoxylsilane, 0.5 g of water, 32 g of propyleneglycolmonomethylether and 0.8 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 64 g of propyleneglycolmonomethylether was added to the reaction mixture. 11 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely at 80 C. The mixture was stirred for 20 hours at 80 C., resulting in a transparent solution with an SC of 23 wt. %.

Inventive Example 18

[0363] 1.76 g of glycidoxypropylmethyldimethoxylsilane, 0.58 g of glycidoxypropyltrimethoxylsilane, 0.5 g of water, 32 g of propyleneglycolmonomethylether and 0.8 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 64 g of propyleneglycolmonomethylether was added to the reaction mixture. 11 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely at 80C. The mixture was stirred for 20 hours at 80C, resulting in a transparent solution with an SC of 21 wt. %.

Inventive Example 19

[0364] Solution 1: Methacryloxypropyltriethoxysilane (120 g) was added to the reaction flask and 21 g water (0.1M HNO.sub.3) was added. The reaction mixture was refluxed at 95 C. in an oil bath for 3 hours and 40 min. The solution was cooled down and mixture of triethylamine (0.39 g) and 2-propanol (3.51 g) was added and refluxing was continued for 65 min. After reflux, solvent was removed under reduced vacuum. Molecular weight of the material was 1000.

[0365] Solution 2. To the Zirkonium (IV) butoxide solution 80% in butanol (400 g) was added Ethylacetoacetate (217.08 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure.

[0366] Mixture preparation: To 1 l round bottom flask was added solution 1 (2.5 g), 1-methoxy-2-propanol (850 g), dipropyleneglycol (50 g), solution 2 (97.5 g) and BYK333 (2.9 g). Solution was mixed at room temperature for 2 hours.

Inventive Example 20

[0367] Solution 1. To the Zirkonium (IV) isopropoxide solution 70% in 2-propanol (50 g) was added Ethylacetoacetate (83.43 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure.

[0368] Solution 2: Methacryloxypropyltriethoxysilane (36 g) was added to the reaction flask and 6.3 g water (0.1M HNO.sub.3) was added. The reaction mixture was stirred at room temperature for 3 days. Solvent removal was done under reduced pressure. Molecular weight of the material was 1000.

[0369] Mixture preparation: To the 500 ml round bottom flask was added solution 1 (77 g), solution 2 (3 g) and Miramer M1142 (20 g). Solution was mixed at room temperature for 2 hours.

Inventive Example 21

[0370] Solution 1. To the Zirkonium (IV) isopropoxide solution 70% in 2-propanol (50 g) was added Ethylacetoacetate (111.24 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure.

[0371] Solution 2: Methacryloxypropyltriethoxysilane (36g) was added to the reaction flask and 6.3 g water (0.1M HNO.sub.3) was added. The reaction mixture was stirred at room temperature for 3 days. Solvent removal was done under reduced pressure. Molecular weight of the material was 1000.

[0372] Mixture preparation: To the 500 ml round bottom flask was added solution 1 (77 g), solution 2 (3 g) and Miramer M1142 (20 g). Solution was mixed at room temperature for 2 hours.

Inventive Example 22

[0373] Solution 1. To the Zirkonium (IV) isopropoxide solution 70% in 2-propanol (50 g) was added Ethylacetoacetate (83.43 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure. Mass of the solution after solvent removal was 96.2 g.

[0374] Solution 2: Methacryloxypropyltriethoxysilane (36 g) was added to the reaction flask and 6.3 g water (0.1 M HNO.sub.3) was added. The reaction mixture was stirred at room temperature for 3 days. Solvent removed was done under reduced pressure. Molecular weight of the material was 1000.

[0375] Mixture preparation: To the 100 ml flask was added solution 1 (67 g), solution 2 (3 g), Miramer M244 (30 g) and BYK3700 (2 g). Solution was mixed 2 hours at room temperature.

Inventive Example 23

[0376] Solution 1. To the Zirkonium (IV) isopropoxide solution 70% in 2-propanol (200 g) was added Ethylacetoacetate (222.48 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure. Mass of the solution after solvent removal was 270.46 g.

[0377] Solution 2: Methacryloxypropyltriethoxysilane (36 g) was added to the reaction flask and 6.3 g water (0.1 M HNO.sub.3) was added. The reaction mixture was stirred at room temperature for 3 days. Solvent removed was done under reduced pressure. Molecular weight of the material was 1000.

[0378] Mixture preparation: To the 100 ml flask was added solution 1 (67 g), solution 2 (3 g), Miramer M1142 (30 g) and BYK3700 (2 g). Solution was mixed 2 hours at room temperature.

Inventive Example 24

[0379] Solution 1. To the Zirkonium (IV) butoxide solution 80% in butanol (1963 g) was added Ethylacetoacetate (1066 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure.

[0380] Solution 2: Miramer 1142 (90 g) was added to the reaction flask, 2-propanol (60 g) and 5.1 g water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours.

[0381] Solution 3. Phenyltrimethoxysilane (5.42 g) was added to the round bottom flask and 1.42 g of water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours.

[0382] Mixture preparation: Solution 2 (155.1 g) and Solution 1 (2372.0 g) were combined. To the combined solution was added 2-methoxy-1-propanol (4145.0 g). Solution 3 (6.9 g) was added to the Solution 1+2. At the end 539.49 g of 2-methoxy-1-propanol was added. Solution was stirred at room temperature for 20 hours.

Inventive Example 25

[0383] Solution 1. To the Zirkonium (IV) butoxide solution 80% in butanol (1963 g) was added Ethylacetoacetate (1066 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure.

[0384] Solution 2: Miramer 1142 (90 g) was added to the reaction flask, 2-propanol (60 g) and 5.1 g water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours.

[0385] Solution 3. Phenyltrimethoxysilane (5.42 g) was added to the round bottom flask and 1.42 g of water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours.

[0386] Mixture preparation: Solution 2 (9.36 g) and Solution 1 (144.0 g) were combined. To the combined solution was added 2-methoxy-1-propanol (252.0 g). Solution 3 (0.41 g) was added to the Solution 1+2. At the end 361.38 g of 2-methoxy-1-propanol was added. Solution was stirred at room temperature over a night.

Inventive Example 26

[0387] Solution 1: To the Zirkonium (IV) butoxide solution 80% in butanol (1963 g), was added Ethylacetoacetate (1066 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure. Solution 2: Miramer 1142 (90 g) was added to the reaction flask, 2-propanol (60 g) and 5.1 g water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours. Solution 3: Phenyltrimethoxysilane (5.42 g) was added to the round bottom flask and 1.42 g of water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours. Mixture preparation: Solution 1 (1244.3 g) and Solution 2 (80.9 g) were combined. To the combined solution was added 2-methoxy-1-propanol (2177.9 g). Solution 3 (3.8 g) was added to the Solution 1+2. At the end 283.2 g of 2-methoxy-1-propanol was added. Solution was stirred at room temperature for 20 hours. Measured viscosity 3.6 mPa-s. Alternatively, instead of solvent PGME, various solvents can be usedfrom single solvents like THF-A (tetrahydrofurfuryl alcohol), PGMEA, Cyclohexanone, Ethylene glycol, Dipropylene glycol monomethyl ether, Diethylene glycol ethyl ether, and their combinations in different ratios.

Inventive Example 27

[0388] Solution 1. To the Zirkonium (IV) butoxide solution 80% in butanol (1963 g), was added Ethylacetoacetate (1066 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure. Solution 2. Miramer 1142 (90 g) was added to the reaction flask, 2-propanol (60 g) and 5.1 g water (0.01M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours. Solution 3: Phenyltrimethoxysilane (5.42 g) was added to the round bottom flask and 1.42 g of water (0.01M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours. Mixture preparation: Solution 1 (268g) and Solution 2 (17.42 g) were combined. To the combined solution was added PGME (2-methoxy-1-propanol, 220.43 g). Amount of 0.50 g of solution 3 was added, and final mixture was stirred at room temperature over a night. Measured viscosity 6.9 mPa-s.

Inventive Example 28

[0389] Solution 1. To the Zirkonium (IV) butoxide solution 80% in butanol (1963 g), was added Ethylacetoacetate (1066 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure. Solution 2. Miramer 1142 (90 g) was added to the reaction flask, 2-propanol (60 g) and 5.1 g water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours. Solution 3: Phenyltrimethoxysilane (5.42 g) was added to the round bottom flask and 1.42 g of water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours. Mixture preparation: Solution 1 (268 g) and Solution 2 (17.42 g) were combined. To the combined solution was added a solvent mixture of PGMEA (1-methoxy-2 propyl acetate, 210.13 g). Amount of 0.50 g of solution 3 was added, and final mixture was stirred at room temperature over a night. Measured viscosity of the solution was 3.9 mPa-s.

Inventive Example 29

[0390] Solution 1. To the Zirkonium (IV) butoxide solution 80% in butanol (1963 g), was added Ethylacetoacetate (1066 g). Solution was mixed at room temperature for 5 days. Solvent removal was done under reduced pressure. Solution 2. Miramer 1142 (90 g) was added to the reaction flask, 2-propanol (60 g) and 5.1 g water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours. Solution 3: Phenyltrimethoxysilane (5.42 g) was added to the round bottom flask and 1.42 g of water (0.01 M HNO.sub.3) was added. Solution was stirred at room temperature for 16 hours. Mixture preparation: Solution 1 (268 g) and Solution 2 (17.42 g) were combined. To the combined solution was added a solvent mixture of PGMEA (1-methoxy-2 propyl acetate, 35.18 g), and Tetrafurfuryl alcohol (82.08 g). Amount of 0.40 g solution 3 was added, and final mixture was stirred at room temperature over a night. Measured viscosity of solution was 20.0 mPa-s.

Inventive Example 30

[0391] 2.34 g of glycidoxypropylmethyldimethoxysilane, 0.5 g of water, 24 g of propyleneglycol monomethylether and 0.2 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 12 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely at 80 C. The mixture was stirred for 3 hours at 100 C. After cooling down to room temperature, 4.6 g of chlorotrimethylsilane was added to the reaction mixture and heated at 100 C. for 1.5 hours, resulting in a transparent solution with an SC of 22 wt. %.

Inventive Example 31

[0392] The procedure of inventive example 30 was repeated except that 2.3 g of chlorotrimethylsilane was used, resulting in a transparent solution with an SC of 21 wt. %.

Inventive Example 32

[0393] 2.34 g of mercaptpropylmethyldimethoxysilane, 0.5 g of water, 24 g of propyleneglycol monomethylether and 0.2 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 14.8 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely at 80 C. The mixture was stirred for 3 hours at 100 C. After cooling down to room temperature, 2.8 g of chlorotrimethylsilane was added to the reaction mixture and heated at 100 C. for 1.5 hours, resulting in a transparent solution with an SC of 19 wt.%.

Inventive Example 33

[0394] 2.34 g of mercaptpropylmethyldimethoxysilane, 0.5 g of water, 24 g of propyleneglycol monomethylether and 0.2 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 7.4 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely at 80 C. The mixture was stirred for 3 hours at 100 C. After cooling down to room temperature, 0.25 g of water and 5.6 g of chlorotrimethylsilane was added to the reaction mixture and heated at 100 C. for 1.5 hours, resulting in a transparent solution with an SC of 17 wt. %.

Inventive Example 34

[0395] 2.34 g of glycidoxypropylmethyldimethoxysilane, 0.5 g of water, 24 g of propyleneglycol monomethylether and 0.2 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 12 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely at 80 C. The mixture was stirred for 3 hours at 100 C. A mixture of 5 g of ethoxytrimethylsilane, 0.5 g of water, 4 g of propyleneglycol monomethylether and 0.2 g of triethylamine was added to the reaction mixture drop-wisely and heated at 100 C. for 15 hours, resulting in a transparent solution with an SC of 16 wt. %.

Inventive Example 35

[0396] 2.34 g of glycidoxypropylmethyldimethoxysilane, 0.5 g of water, 24 g of propyleneglycol monomethylether and 0.2 g of triethylamine were placed in a round bottom flask and stirred for 30 min at 80 C. (oil bath). 12 g of tetraisopropylorthotitanate was added to the reaction mixture drop-wisely at 80 C. The mixture was stirred for 3 hours at 100 C. A mixture of 6.3g of diethoxydimethylsilane, 0.5 g of water, 4g of propyleneglycol monomethylether and 0.2 g of triethylamine was added to the reaction mixture drop-wisely and heated at 100 C. for 18 hours, resulting in a transparent solution with an SC of 17 wt. %.

Application Example 19

[0397] the thin film coating material of inventive example 19 was deposited on glass by spray coating method. Coating material solid content was about 9.8%. The spray coat parameters to deposit the layer on Gorilla glass 4 are following: Scan speed: 300 mm/s, Pitch: 50 mm, Gap: 50-100 mm, Flow rate: 3-10 ml/min, Atomization air pressure: 5 kg/cm.sup.2. After spray deposition the films were cured in convection oven at 150C for 30 min. FIG. 4 shows the transmission graph of the resulting material. The reflection and absorption of the glass substrate is not subtracted. Other optical properties of the film include: 92.3% transmission at 550 nm, a*(D65) 0.07 and b*(D65) 0.46. Refractive Index was 1.56 (at 632 nm) and final cured thickness 308 nm.

Application Example 20

[0398] The material of inventive example 20 was tested by characterizing the material on silicon wafer (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: <1-0-0>, Resistivity: 1-30 ohm.Math.cm, Thickness: 675+/25 m, TTV: <5 m, Particle: <20@0.2 m, Front Surface: Polished, Back Surface: Etched, Flat:1 SEMI Standard) and spin coating was used as deposition method in this case. Spin coating at 2000 rpm was used as deposition process, pre-bake at 100 C. for 120 sec, Post-bake at 100 C. for 30 min. Film thickness was measured to be 3.1 m and Refractive index 1.608 (at 632 nm).

Application Example 21

[0399] The material of inventive example 21 was tested by characterizing the material on silicon wafer (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: <1-0-0>, Resistivity: 1-30 ohm.Math.cm, Thickness: 675+/25 m, TTV: <5 m, Particle: <20@0.2 m, Front Surface: Polished, Back Surface: Etched, Flat:1 SEMI Standard) and spin coating was used as deposition method in this case. Spin coating at 2000 rpm was used as deposition process, pre-bake at 100 C. for 120 sec, Post-bake at 100 C. for 30 min. Film thickness was measured to be 3.3 m and Refractive index 1.613 (at 632 nm).

Application Example 22

[0400] The material of inventive example 22 was tested by characterizing the material on silicon wafer (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: <1-0-0>, Resistivity: 1-30 ohm.Math.cm, Thickness: 675+/25 m, TTV: <5 m, Particle: <20@0.2 m, Front Surface: Polished, Back Surface: Etched, Flat:1 SEMI Standard) and spin coating was used as deposition method in this case. Spin coating at 2000 rpm was used as deposition process, pre-bake at 100 C. for 120 sec, Post-bake at 100 C. for 30 min. Film thickness was measured to be 6.1 m and Refractive index 1.585 (at 632 nm).

Application Example 23

[0401] The material of inventive example 23 was tested by characterizing the material on silicon wafer (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: <1-0-0>, Resistivity: 1-30 ohm.Math.cm, Thickness: 675+/25 m, TTV: <5 m, Particle: <20@0.2 m, Front Surface: Polished, Back Surface: Etched, Flat: 1 SEMI Standard) and spin coating was used as deposition method in this case. Spin coating at 2000 rpm was used as deposition process, pre-bake at 100 C. for 120 sec, Post-bake at 100 C. for 30 min. Film thickness was measured to be 6.1 m and Refractive index 1.653 (at 632 nm).

Application Example 24

[0402] The thin film coating material of inventive example 24 was deposited on S2003F3, from Matsunami Glass Ind., Ltd. by spin coating at 360 rpm for 30 seconds with a spin-coater, 1H-DX2, from Mikasa Co., Ltd., Japan. Pre-bake 100 C. 120 sec, Post-bake 250 C. 30 min. Film thickness was measured to be 200 nm and Refractive index 1.71 (at 632 nm). Then 1-bromonaphthalene from Wako Pure Chemical Industries, Ltd., Japan was additionally applied on the surface of the coating at the thickness of 58 um to eliminate thin film interference effect for the transmittance measurement and covered with same slide glass plate. FIG. 5 shows the transmission graph of the material. Other optical properties of the thin film include (substrate excluded): 99.1% transmission at 550 nm, a*(D65) 0.35 and b*(D65) 0.45.

Application Example 24A

[0403] The procedure of application example 24 was repeated except that the post bake step was performed four (4) times at 250 C. for 30 min with cooling to room temperature between each baking step.

Application Example 24B

[0404] The procedure of application example 24 was repeated except that the post bake step was performed at 250 for 30 min and subsequently at 350 C. for 30 min.

[0405] The results are given in the following table.

TABLE-US-00001 refractive Average Transmission Thickness index (360-740 nm [%] [nm Application example 24 1.71 96.8 463 Application example 24A 1.75 95.8 393 Application example 24B 1.87 92.2 301

[0406] In above table a summary is given on single bake and multi-bake cycle stability for the material. The refractive index varied from 1.71-1.87 when increasing the bake temperature, and film thickness decreased from 463 nm to 301 nm.

[0407] Furthermore, the outgassing of application example 24 was determined by Thermogravimetric analysis (TGA). The results are shown in FIG. 6 and summarized in the following table.

TABLE-US-00002 weight change change vs. result compared with of previous phase Phase t = 0 min [wt. %] [wt. %] 1 (after 60 min holding 97.3 2.7 time at 160 C.) 2 (after 60 min holding 96.0 1.3 time at 230 C.) 3 (after 30 min holding 94.7 1.3 time at 250 C.)

[0408] FIG. 6 and the table above show that the material has a low weight loss even under elevated temperatures determined by thermal gravimetry analysis (TGA) for the Example 24 material. The weight loss at 160 C. is attributed to the removal of trace amounts of water. After the removal of water, at 230 C. as well as at 250 C. no significant weight loss was observed. These are typical process temperatures in device fabrication. Thus, the inventive material generates no significant outgassing during production process.

Application Example 24C

[0409] The procedure of application example 24 was repeated except that the spin coating step was performed at 2000 rpm.

[0410] The thickness of the obtained films of application example 24 and application example 24C during the course of 23 weeks at +4 C. and +23 C. was determined. For application example 24 the differences in refractive index at +4 C. and +23 C. was also determined. The results are shown in the following tables.

[0411] Thickness of the film of application example 24 [nm]

TABLE-US-00003 0 days 5 weeks 10 weeks 23 week +4 C. 458 452 422 467 +23 C. 458 424 440 451

[0412] Thickness of the film of application example 24C [nm]

TABLE-US-00004 0 days 5 weeks 10 weeks 23 week +4 C. 223 214 200 218 +23 C. 223 196 202 215

[0413] Refractive index of the film of application example 24

TABLE-US-00005 0 days 5 weeks 10 weeks 23 week +4 C. 1.710 1.707 1.710 1.71 +23 C. 1.710 1.709 1.707 1.70

[0414] The data in the tables above represent shelf-life stability data for the material of inventive example 24. Ready to use formulation shelf-life has been analyzed at +4 C. and +23. Two different spin speed and resulting film thicknesses were analyzed in terms of film thickness consistency and refractive index consistency during the period of 23 weeks. From the data it can be confirmed that the material of inventive example 24 is very stabile at both ageing temperatures.

Application Example 25

[0415] The thin film coating material of inventive example 25 was deposited on Gorilla glass 4 by spin coating method. The material was characterized on glass substrate and spin coating was used as deposition method. Spin coating at 2000 rpm was used as deposition process, pre-bake 100 C. 120 sec, Post-bake 250 C. Film thickness was measured to be 56 nm and Refractive index 1.72 (at 632 nm). The only difference between Example 24 and 25 material is the further dilution of the material in case of sample 25 to result in thinner film.

Application Example 27

[0416] The thin film coating material of inventive example 26 was tested by characterizing the material on Gorilla Glas 4 and spin coating was used as deposition method in this case. Spin coating at 2000 rpm was used as deposition process, pre-bake at 100 C. for 120 sec, Post-bake at 250 C. for 30 min.

Application Example 28

[0417] The procedure of application example 27 was repeated except that inventive material 28 was used.

[0418] The results are shown in the following table

TABLE-US-00006 Application Application example 27 example 28 thickness [nm] 409 408 refractive index (632 nm) 1.71 1.71 a* 0.32 0.3 b* (yellowing) 0.45 0.74 L* 95.58 95.52 transmission (400 nm) [%] 87.89 87.04 transmission (550 nm) [%] 88.25 87.86

Application Example 28A

[0419] The thin film coating material of inventive example 28 was deposited on glass by ink-jet printing coating method. The material was characterized on Gorilla glass 4 and silicon wafers (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: <1-0-0>, Resistivity: 1-30 ohm.Math.cm, Thickness: 675+/25 m, TTV: <5 m, Particle: <20@0.2 m, Front Surface: Polished, Back Surface: Etched, Flat: 1 SEMI Standard) and ink-jet coating was used as deposition method. Ink-jet printing (Dimatix Materials Printer DMP-2850; Jets 16, jetting frequency 5 kHz, applied voltage 20V, drop spacing 30 m, cartridge type 10 pL) was used as deposition process, pre-bake at 100 C. for 120 sec, Post-bake at 250 C. for 30 minutes. Film thickness was measured to be 450 nm and Refractive index 1.71 (at 632 nm).

Application Example 28B and C

[0420] The thin film coating material of inventive example 28 was further modified by introducing scatter particles (TiO.sub.2 with an average particle size of 200 nm, obtainable from Kronos) in to the material at two different concentrations. Application example 28B was prepared by adding 3.8 weight-% of the scatter particles by weight to the inventive example 28 formulation and application example 28C was prepared by adding 4.8 weight-% of the scatter particles into the inventive example 28 formulation. The thin film coating material of inventive example 28B and 28C were deposited on Gorilla glass 4 by spin coating method. Spin coating at 400 rpm was used as deposition process, pre-bake at 100 C. for 120 sec, Post-bake at 250 C. for 30 minutes. Film thickness was measured to be 400 nm. Other optical data of the two application examples listed in the below table.

TABLE-US-00007 Application Application example 28B example 28C thickness [nm] 400 400 Haze 15% 18% a* 1.21 2.52 b* (yellowing) 0.72 0.47 L* 71.57 61.45 transmission (400 nm) [%] 50.59 36.10 transmission (550 nm) [%] 46.44 31.81

Comparative Example 1 (vs. Inventive Example 1-18)

[0421] 0.5 g of water, 24 g of propyleneglycolmonomethylether and 0.2g of triethylamine were placed in a round bottom flask and heated at 80 C. (oil bath). A mixture of 2.34 g of methacryloxypropylmethyldimethoxysilane and 5.2 g of tetraisopropylorthotitanat was added to the reaction mixture drop-wisely (3 min) at 80 C. Precipitates gradually generated during the addition and the solution became semi-transparent after addition of the mixture. The reaction mixture was stirred for 3 hours at 80C, giving a semi-transparent white dispersion. A film was not formed from this composition, because an opaque film will result.