Substrate structure and method for preparing the same

Abstract

The present invention relates to a substrate structure in which organic-inorganic hybrid thin films are laminated and a method for preparing the same and more specifically to a substrate structure in which organic-inorganic hybrid thin films are laminated that can be used for light emitters, display devices and solar cell devices wherein the organic-inorganic hybrid thin film including a stable new functional group, an inorganic precursor and an organic precursor are alternately used to afford stability in air and a method for preparing the same.

Claims

1. A substrate structure comprising: a substrate; and hybrid organic/inorganic thin films stacked on the substrate, the hybrid organic/inorganic thin films being represented by the following Formula 1:
-[M-XR1-Y]m-[Formula 1] wherein in Formula 1, m is 1 or more, R1 is a substituted or unsubstituted aryl or heteroaryl having a nuclear atomic number of 5-60, M is selected from the group consisting of Zn, Sn, In, Cd, Ga, Al, Ti, Si, V, Mn, Fe, Co, Cu, Zr, Ru, Mo, Nb, and W, one of X and Y is O, and the other is S.

2. The substrate structure of claim 1, wherein a thickness of the hybrid organic/inorganic thin films is from 1 to 500 .

3. The substrate structure of claim 1, wherein the following relationship is satisfied when an initial thickness of the hybrid organic/inorganic thin films is set to do, and a thickness of the hybrid organic/inorganic thin films after standing under STP conditions for n hours is set to dn:
0(dn/d0)0.1(0n240), wherein d0 and dn are measured under STP conditions.

4. The substrate structure comprising functional thin films comprising the hybrid organic/inorganic thin films as claimed in claim 1 and further comprising an oxide layer of a metal selected from the group consisting of Zn, Sn, In, Cd, Ga, Al, Ti, Si, V, Mn, Fe, Co, Cu, Zr, Ru, Mo, Nb, and W, formed on or under the hybrid organic/inorganic thin films.

5. The substrate structure of claim 4, wherein a thickness of the oxide layer of a metal is from 100 to 2,000 .

6. The substrate structure of claim 4, wherein the following relationship is satisfied when an initial thickness of the substrate structure is set to D0, and a thickness of the substrate structure after standing under STP conditions for n hours is set to Dn:
0(Dn/D0)0.1(0n240), wherein d0 and do are measured under STP conditions.

7. The substrate structure of claim 1, wherein the substrate is a conductive and transparent substrate selected from the group consisting of ITO, FTO, ZnO, AZO, CdO, and TiO.sub.2.

8. The substrate structure of claim 1, wherein the substrate is a polymer substrate selected from the group consisting of a fluoropolymer resin, polyester, polyacrylate, polyamide, polyimide, and polycarbonate.

9. A light-emitting body comprising the substrate structure as claimed in claim 1.

10. A display apparatus comprising the substrate structure as claimed in claim 1.

11. A photovoltaic device comprising the substrate structure as claimed in claim 1.

12. A method of manufacturing a substrate structure as claimed in claim 1, the method comprising: (1) forming an inorganic molecular layer on a surface of a substrate using a first precursor compound represented by the following Formula 2:
M(R21)(R22) . . . (R2n)[Formula 2] wherein in Formula 2, M is selected from the group consisting of Zn, Sn, Cd, Ti, Si, V, Mn, Fe, Co, Cu, Zr, Ru, Mo, Nb, W, In, Ga, Al, and Tl, n is determined as claimed in an oxidation number of a metal M, and R21 to R2n are each independently C.sub.1-20 alkyl, C.sub.1-20 alkoxide, a chloride group, a hydroxyl group, an oxyhydroxide group, a nitrate group, a carbonate group, an acetate group, or an oxalate group; and (2) forming an organic molecular layer on the inorganic molecular layer via a reaction of a second precursor compound represented by the following Formula 3 with the inorganic molecular layer:
R3-SR4-R5[Formula 3] wherein in Formula 3, R3 is hydrogen, COR6, C.sub.1-20 alkyl, C.sub.5-20 cycloalkyl, or aryl or heteroaryl of nuclear atomic number of 5-60, R4 is C.sub.1-20 alkyl, C.sub.5-20 cycloalkyl, or aryl or heteroaryl of nuclear atomic number of 5-60, R5 is at least one selected from the group consisting of a hydroxyl group, a C.sub.1-20 alkoxy group, an ether group, a carboxyl group, COR6, a thiol group, and an amine group, and R6 is at least one selected from the group consisting of hydrogen, an alkoxy group, an ether group, a carboxyl group, a thiol group, and an amine group.

13. The method of manufacturing a substrate structure of claim 12, wherein the second precursor compound is represented by the following Formula 4: ##STR00003## wherein in Formula 4, Z is a thiol group, Q is one selected from a thiol group or a hydroxyl group, and Z and Q are at an ortho, meta, or para position.

14. The method of manufacturing a substrate structure as claimed in claim 13, wherein the second precursor compound is represented by the following Formula 5: ##STR00004##

15. The method of manufacturing a substrate structure as claimed in claim 13, wherein the second precursor compound is represented by the following Formula 6: ##STR00005##

16. The method of manufacturing a substrate structure as claimed in claim 12, further comprising repeatedly conducting (1) and (2).

17. The method of manufacturing a substrate structure as claimed in claim 12, further comprising forming an oxide layer on a surface of the substrate prior to (1).

18. The method of manufacturing a substrate structure having functional thin films of claim 12, the method further comprising (3) forming an oxide layer of a metal selected from the group consisting of Zn, Sn, In, Cd, Ga, Al, Ti, Si, V, Mn, Fe, Co, Cu, Zr, Ru, Mo, Nb, and W by an atomic layer deposition method.

19. The method of manufacturing a substrate structure of claim 12, that comprises repeatedly conducting (1) and (2) n1 times where n1 is 1 or more, and then, (3) n2 times wherein n2 is 1 or more.

20. The method of manufacturing a substrate structure of claim 19, comprising repeatedly conducting (1) to (3).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 to FIG. 6 schematically show the substrate structures according to examples of the present invention.

(2) FIG. 7 and FIG. 8 respectively show thin film growth rates versus the injection amounts of first precursor and second precursor in one example of the present invention.

(3) FIG. 9 shows results of the ultraviolet spectroscopic measurement on the organic-inorganic hybrid thin film and 4-mercapto phenol prepared in one example of the present invention.

(4) FIG. 10 shows results of the UV-Vis absorption measurement on the organic-inorganic hybrid thin film prepared in one example of the present invention.

(5) FIG. 11 shows results of the air stability test on the organic-inorganic hybrid thin film prepared in one example of the present invention and the thin film prepared in the comparative example.

(6) FIG. 12 shows results of the thin film thickness measurement versus the cycle of the organic-inorganic hybrid thin film formation process in one example of the present invention.

(7) FIG. 13 shows results of the surface roughness measurement on the hybrid thin film prepared in one example of the present invention.

(8) FIG. 14 and FIG. 15 respectively show thin film growth rates versus the injection amounts of first precursor and second precursor in one example of the present invention.

(9) FIG. 16 shows results of the ultraviolet spectroscopic measurement on the organic-inorganic hybrid thin film prepared in one example of the present invention.

(10) FIG. 17 shows results of the UV-Vis absorption measurement on the organic-inorganic hybrid thin film prepared in one example of the present invention.

(11) FIG. 18 shows results of the air stability test on the organic-inorganic hybrid thin film prepared in one example of the present invention and the thin film prepared in the comparative example.

(12) FIG. 19 shows results of the thin film thickness measurement of the organic-inorganic hybrid thin film formation process in one example of the present invention.

(13) FIG. 20 shows results of the surface roughness measurement on the hybrid thin film prepared in one example of the present invention.

(14) FIG. 21 shows results of the TEM photograph measurement on the organic-inorganic hybrid super-lattice thin film prepared in one example of the present invention.

(15) FIG. 22 and FIG. 23 show the rate of pinhole formation inhibition measured by varying the thickness of an organic-inorganic hybrid thin film in the organic-inorganic hybrid super-lattice thin film prepared in one example of the present invention.

(16) FIG. 24 shows results of the thin film stress measurement versus the ratio of the Al.sub.2O.sub.3 thin film formed by atomic layer deposition to the organic-inorganic hybrid thin film in the organic-inorganic hybrid super-lattice thin film prepared in one example of the present invention.

(17) FIG. 25 shows results of the Ca test on the organic-inorganic hybrid thin film prepared in one example of the present invention and the thin film prepared in the comparative example.

SPECIFIC DETAILS FOR IMPLEMENTING THE INVENTION

(18) The present invention is described in further detail below according to examples of the present invention. However, the present invention is not limited to the examples below.

Example 1

(19) After an Si (100) substrate was washed with distilled water and acetone, it was purged with N.sub.2 gas 2-3 times to remove any contaminants on the substrate surface before diethyl zinc (DEZn) was used as a first precursor compound to deposit a diethyl zinc (DEZn) thin film over the Si substrate according to the molecular layer deposition method.

(20) Over the diethyl zinc (DEZn) thin film was formed an organic molecular film by using 4-mercapto phenol as a second precursor compound according to the molecular layer deposition method to prepare an organic-inorganic hybrid thin film. Argon was used for both carrier gas and purging gas, and DEZn and 4-mercapto phenol were respectively evaporated at 20 C. and 70 C. One cycle was achieved by exposure to DEZn for 2 seconds, purging with Ar for 10 seconds, exposure to 4-mercapto phenol for 2 seconds and purging with Ar for 50 seconds. The thin film was grown at a temperature of 80 C. to 200 C. and under a pressure of 300 mTorr.

(21) <Experiment> Measurement of Growth Rates Versus Injection Time of Organic Precursor and Inorganic Precursor

(22) In Example 1, growth rates of the thin film according to the injection time of the first precursor compound of diethyl zinc (DEZn) and growth rates of the thin film according to the injection time of the second precursor compound of 4-mercapto phenol were measured and respectively shown in FIG. 7 and FIG. 8.

(23) It may be noted from FIG. 7 and FIG. 8 that growth rates of the thin films increased with injection amounts of the first precursor compound of diethyl zinc (DEZn) and the second precursor compound of 4-mercapto phenol and then the growth rates no longer increased but remained at certain rates.

(24) <Experiment> IR Spectroscopic Measurement

(25) IR spectroscopic measurements were made on the organic-inorganic hybrid thin film prepared by the same method as Example 1 except that KBr pellets were used instead of the Si substrate and 4-mercapto phenol, and the results are shown in FIG. 9.

(26) It may be verified in FIG. 9 that a hydroxyl group and a thiol group of 4-mercapto phenol are found in the comparative example in which only 4-mercapto phenol is included whereas in the case of the organic-inorganic hybrid thin film according to the present invention, the hydroxyl group and the thiol group of mercapto phenol used as its second precursor react with the inorganic molecular layer prepared by its first precursor to form a hybrid thin film so that the hydroxyl group and thiol group of mercapto phenol are not detected by the infrared spectroscopic method.

(27) <Experiment> UV-VIS Spectroscopic Measurement

(28) UV-Vis absorption on the organic-inorganic hybrid thin film prepared in Example 1 above was measured and the results are shown in FIG. 10. It may be verified from FIG. 10 that the organic-inorganic hybrid thin film according to the present invention has no absorption in the visible ray range.

Comparative Example

(29) In a comparative example an organic-inorganic hybrid thin film was prepared the same way as in Example 1 above except that diethyl zinc (DEZn) was used as its first precursor compound to deposit a diethyl zinc (DEZn) thin film oven an Si substrate according to the molecular layer deposition method and then hydroquinone (HQ) was used as its second precursor compound.

(30) <Experiment> Stability Test in Air

(31) While the organic-inorganic hybrid thin film of Example 1 and the organic-inorganic hybrid thin film prepared in the Comparative Example above were left in air, changes in their thicknesses were measured to test stability in air, and the results are shown in FIG. 11.

(32) It may be realized in FIG. 11 that unlike in the present invention the thickness drastically decreases in the case of the Comparative Example that does not include an S group whereas the thickness does not change with time in the case of the Example according to the present invention and that the organic-inorganic hybrid multi-layered film including an S group is very stable in air.

Example 2

(33) As in Example 1 above, diethyl zinc (DEZn) was used as the first precursor compound to deposit a thin film over an Si substrate and 4-mercapto phenol was used as the second precursor compound to form an organic-inorganic hybrid thin film over the diethyl zinc (DEZn) thin film according to the molecular layer deposition method before the process of forming the diethyl zinc (DEZn) by the first precursor compound, and while the thin film based on the second precursor compound was repeatedly formed, thicknesses of the thin film were measured and the results are shown in FIG. 12.

(34) It may be verified in FIG. 12 that the number of repetitions for the process of forming the thin film by the first precursor compound and forming the thin film by the second precursor compound is proportional to the thickness of the thin film formed.

(35) <Experiment> Surface Roughness Measurement

(36) The organic-inorganic hybrid thin film of 50 nm in the thickness prepared in Example 2 was measured for its surface roughness with AFM, and the results are shown in FIG. 13. The average roughness measured was 2.2 A.

Example 3

(37) After an Si (100) substrate was washed with distilled water and acetone, it was purged with N.sub.2 gas 2-3 times to remove any contaminants on the substrate surface before trimethyl aluminium (TMA) was used as a first precursor compound to deposit a trimethyl aluminium (TMA) thin film over the Si substrate according to the molecular layer deposition method.

(38) Over the trimethyl aluminium (TMA) thin film was formed an organic molecular film by using 4-mercapto phenol as a second precursor compound according to the molecular layer deposition method to prepare an organic-inorganic hybrid thin film.

(39) Argon was used for both carrier gas and purging gas, and TMA and 4-mercapto phenol were respectively evaporated at 20 C. and 70 C. One cycle was achieved by exposure to TMA for 2 seconds, purging with Ar for 10 seconds, exposure to 4-mercapto phenol for 2 seconds and purging with Ar for 50 seconds. The thin film was grown at a temperature of 80 C. to 200 C. and under a pressure of 300 mTorr.

(40) <Experiment> Measurement of Growth Rates Versus Injection Time of Organic Precursor and Inorganic Precursor

(41) In Example 3, growth rates of the thin film according to the injection time of the first precursor compound of trimethyl aluminium (TMA) and growth rates of the thin film according to the injection time of the second precursor compound of 4-mercapto phenol were measured and respectively shown in FIG. 14 and FIG. 15.

(42) It may be noted from FIG. 14 and FIG. 15 that growth rates of the thin films increased with injection amounts of the first precursor compound of trimethyl aluminium (TMA) and the second precursor compound of 4-mercapto phenol and then the growth rates no longer increased but remained at certain rates.

(43) <Experiment> IR Spectroscopic Measurement

(44) IR spectroscopic measurements were made on the organic-inorganic hybrid thin film prepared by the same method of Example 3 except that KBr pellets were used instead of the Si substrate and 4-mercapto phenol, and the results are shown in FIG. 16.

(45) It may be verified in FIG. 16 that in the case of the organic-inorganic hybrid thin film according to the present invention, the hydroxyl group and the thiol group of mercapto phenol used as its second precursor react with the inorganic molecular layer prepared by its first precursor to form a hybrid thin film so that the hydroxyl group and the thiol group of mercapto phenol are not detected by the infrared spectroscopic method.

(46) <Experiment> UV-VIS Spectroscopic Measurement

(47) UV-Vis absorption on the organic-inorganic hybrid thin film prepared in Example 3 above was measured and the results are shown in FIG. 17. It may be verified from FIG. 17 that the organic-inorganic hybrid thin film according to the present invention has no absorption in the visible ray range.

Comparative Example

(48) In a comparative example an organic-inorganic hybrid thin film was prepared in the same way as in Example 3 above except that trimethyl aluminium (TMA) was used as its first precursor compound to deposit a trimethyl aluminium (TMA) thin film oven an Si substrate according to the molecular layer deposition method and then hydroquinone (HQ) was used as its second precursor compound.

(49) <Experiment> Stability Test in Air

(50) While the organic-inorganic hybrid thin film of Example and the organic-inorganic hybrid thin film prepared in the Comparative Example above were left in air, changes in their thicknesses were measured to test stability in air, and the results are shown in FIG. 18.

(51) It may be recognized in FIG. 12 that, assuming that the initial thickness is d0 and the thickness in n hours is dn, dn/d0 in the case of the Comparative Example without including the S group increases to 0.5 or more as a result of a drastic decrease in its thickness unlike in the present invention whereas in the case of the Example according to the present invention, dn/d0 is kept at 0.1 or less as a result of the absence of changes in its thickness with time and that the organic-inorganic hybrid thin film according to the present invention is very stable in air.

Example 4

(52) As in Example 3 above, trimethyl aluminium (TMA) was used as the first precursor compound to deposit a thin film over an Si substrate and 4-mercapto phenol was used as the second precursor compound to form an organic-inorganic hybrid thin film over the trimethyl aluminium (TMA) thin film according to the molecular layer deposition method before the process of forming the trimethyl aluminium (TMA) thin film by the first precursor compound, and while the thin film based on the second precursor compound was repeatedly formed, thicknesses of the thin film were measured and the results are shown in FIG. 19.

(53) It may be verified in FIG. 19 that the number of repetitions for the process of forming the thin film by the first precursor compound and forming the thin film by the second precursor compound is proportional to the thickness of the thin film formed.

(54) <Experiment> Surface Roughness Measurement

(55) The organic-inorganic hybrid thin film of 50 nm in the thickness prepared in Example 4 was measured for its surface roughness with AFM, and the results are shown in FIG. 20. The average roughness measured was 2.8 A.

Example 5

(56) After an organic-inorganic hybrid thin film was prepared in the same way as in Examples 1 and 3 above, an Al.sub.2O.sub.3 thin film was deposited over the organic-inorganic hybrid thin film according to the atomic layer deposition method, and such a process was repeated by controlling the ratio of the Al.sub.2O.sub.3 thin film based on atomic layer deposition to the organic-inorganic hybrid thin film according to the present invention to prepare an organic-inorganic hybrid functional thin film.

(57) In order to form the Al.sub.2O.sub.3 thin film according to atomic layer deposition, argon gas was used as carrier gas and purging gas, and trimethyl aluminium (TMA) and H.sub.2O were evaporated at normal temperature. Its cycle was achieved by exposure to TMA for 1 second, purging with Ar for 5 seconds, exposure to H.sub.2O for 1 second and purging with Ar for 5 seconds. The above thin film was grown at a temperature of 80 C. under a pressure of 300 mTorr.

(58) <Experiment> TEM Measurement

(59) The TEM photograph was measured when the ratio of the organic-inorganic hybrid thin film:Al.sub.2O.sub.3 thin film prepared in Example 5 above was 1:2, and the results are shown in FIG. 21. It may be verified in FIG. 21 that the Al.sub.2O.sub.3 thin film according to atomic layer deposition and the organic-inorganic hybrid thin film according to the present invention were alternately formed.

(60) <Experiment> Measurement of Pinhole Formation Inhibition Effects

(61) In Example 5 above, rates of pinhole formation inhibition were measured by varying the thickness of the organic-inorganic hybrid thin film, and the results are shown in FIG. 22 and FIG. 23.

(62) It may be realized in FIG. 23 that pinholes are seldom formed if the thickness of the organic-inorganic hybrid thin film according to the present invention is 80 nm or more.

(63) <Experiment> Thin Film Stress Measurement

(64) In the organic-inorganic hybrid functional thin film prepared in Example 5 above, thin film stress was measured versus the ratio of the Al.sub.2O.sub.3 thin film to the organic-inorganic hybrid thin film according to the present invention while the total thickness of the thin film was kept the same, and the results are shown in FIG. 24.

(65) <Experiment> Measurements of Moisture Permeability Resistance and Oxygen Permeability Resistance

(66) The organic-inorganic hybrid functional thin film prepared in Example 5 above, and the Al.sub.2O.sub.3 thin film of the Comparative Example were measured for their moisture permeability resistance and oxygen permeability resistance, and the results are listed in Table 1 and FIG. 25 below.

(67) It may be noted from Table 1 and FIG. 25 below that the functional thin film comprising the organic-inorganic hybrid thin film and Al.sub.2O.sub.3 according to the present invention has superior moisture permeation resistance and oxygen permeation resistance to those of the Comparative Example.

(68) TABLE-US-00001 TABLE 1 Barrier Film WVTR OTR (nm) (g/m.sup.2 day) (cm.sup.3/m.sup.2 day) Al.sub.2O.sub.3 3.11 10.sup.7 9.66 10.sup.5 (100 nm) Organic/Al.sub.2O.sub.3 super lattice 2.68 10.sup.7 8.33 10.sup.5 (100 nm)

INDUSTRIAL VIABILITY

(69) Because the substrate structure comprising the organic-inorganic hybrid thin film according to the present invention includes a new functional group so as to remain stable in air, it can be not only used for encapsulation of light emitters, displays and solar battery cells but also applied to various fields including nano patterning for manufacturing semiconductors and electronic devices, chemical sensors and biosensors, nano tribology, surface modification, nano electronic machine systems (NEMS), micro electronic machine systems (MEMS) and non-volatile memory.

(70) The method for preparing the organic-inorganic hybrid thin film according to the present invention enables provision of a very stable organic-inorganic hybrid multi-layered molecular film in air by including a new functional group not used previously in its organic precursor when preparing the organic-inorganic hybrid thin film by alternately using organic precursor and inorganic precursor according to the molecular layer deposition method.