Process for the generation of thin inorganic films

Abstract

Processes for the generation of thin inorganic films on substrates, in particular atomic layer deposition processes. In particular, a process of bringing a compound of general formula (I) into the gaseous or aerosol state
L.sub.n - - - M - - - X.sub.m(I)
and depositing the compound of general formula (I) from the gaseous or aerosol state onto a solid substrate, wherein
M is a metal,
L is a ligand which coordinates to M and contains at least one phosphorus-carbon multiple bond, wherein L contains a phosphorus-containing heterocyclic ring or a phosphorus-carbon triple bond,
X is a ligand which coordinates to M,
n is 1 to 5, and
m is 0 to 5.

Claims

1. A process, comprising bringing a compound selected from the group consisting of formula (Ia), formula (Ib), and a dimer of formula (Ic) into
L.sub.n - - - M - - - X.sub.m(I) and depositing the compound from a gaseous or aerosol state onto a solid substrate, wherein: the compound of formula (Ia) is ##STR00010## wherein R.sup.1 and R.sup.2 are each independently nothing, hydrogen, an alkyl group, an aryl group or a silyl group, wherein R.sup.3 and R.sup.4 are each independently an alkyl group, an aryl group or a silyl group, the compound of formula (Ib) is ##STR00011## wherein R.sup.5 is nothing, hydrogen, an alkyl group, an aryl group or a silyl group, and wherein R.sup.6 to R.sup.9 are each independently hydrogen, an alkyl group, an aryl group or a silyl group, the dimer of formula (Ic) is ##STR00012## wherein R.sup.5 is an alkyl group, an aryl group or a silyl group M is a metal, X is a ligand which coordinates to M, n is 1 to 5, and m is 0 to 5.

2. The process according to claim 1, wherein the compound is formula (Ia) ##STR00013##

3. The process according to claim 1, wherein the compound is formula (Ib) ##STR00014##

4. The process according to claim 1, wherein the compound is the dimer of formula (Ic) ##STR00015##

5. The process according claim 1, wherein M is Ni, Co, Mn, Ti, Ta or W.

6. The process according to claim 1, wherein at least one X is a cyclopentadienyl derivative.

7. The process according to claim 1, wherein at least one X is CO.

8. The process according to claim 1, wherein the compound is chemisorbed on a surface of the solid substrate.

9. The process according to claim 1, wherein the deposited compound is decomposed by removal of all ligands L and X.

10. The process according to claim 1, wherein the deposited compound is exposed to a reducing agent.

11. The process according to claim 1, wherein a sequence of depositing the compound onto a solid substrate and decomposing the deposited compound is performed at least twice.

Description

EXAMPLES

Example 1

(1) ##STR00004##

(2) Compound Ia-1 was synthesized according to the procedure by Wolf et al. in Angewandte Chemie International Edition volume 47 (2008), page 4584. It sublimes at 90 to 100 C. at 10.sup.2 mbar, its melting point is 193 C.

(3) FIG. 1 shows the thermogravimetric analysis data of Ia-1. The residual mass at 500 C. is 27%.

Example 2

(4) ##STR00005##

(5) Compound Ia-2 was synthesized according to the procedure by Wolf et al. in Angewandte Chemie International Edition volume 47 (2008), page 4584. It sublimes at 90 to 100 C. at 10.sup.2 mbar, its melting point is 185 C.

(6) FIG. 2 shows the thermogravimetric analysis data of Ia-1. The residual mass at 500 C. is 37%.

Example 3

(7) ##STR00006##

(8) Compound Ia-3 was synthesized according to the procedure by Wolf et al. in Chemistry, A European Journal, volume 16 (2010), page 14322. It sublimes at 100 C. at 10.sup.2 mbar, its melting point is 196 C.

(9) FIG. 3 shows the thermogravimetric analysis data of Ia-3. The residual mass at 500 C. is 38%.

Example 4

(10) ##STR00007##

(11) A solution of Me.sub.3SiCl in toluene (0.15 M, 0.87 mmol, 5.7 mL) was added to a solution of [K(thf).sub.2{Co(P.sub.2C.sub.2tBu.sub.2).sub.2}] (0.43 g, 0.79 mmol) in toluene (30 mL) at room temperature. The reaction mixture was stirred overnight whereupon a dark red solution was formed. The solvent was then removed in vacuo and the deep red residue was extracted with n-pentane (20 mL). Concentrating the red extract to ca. 10 mL and storage at 30 C. for two days gave red crystals of Ia-4. Yield: 0.24 g (58%). It was found that compound Ia-4 contains a variable amount of [Co(P.sub.2C.sub.2tBu.sub.2).sub.2H] (Ia-3). The contamination was determined to be ca. 4% according to the .sup.1H NMR spectrum.

(12) .sup.1H NMR (400.13 MHz, C.sub.6D.sub.6): =0.28 (d, J(H,P)=7.0 Hz, 9H, SiMe.sub.3), 1.24 (s, 18H, tBu), 1.30 (s, 18H, tBu);

(13) .sup.31P{.sup.1H} NMR (161.98 MHz, C.sub.6D.sub.6): =1.9 (s, 1P), 19.3 (s, 1P), 21.8 (s, 2P). The NMR shifts are similar to the known complex [Co(P.sub.2C.sub.2tPent.sub.2SiMe.sub.3)(P.sub.2C.sub.2tPent.sub.2)] with tPent instead of tBu substituents.

(14) Compound Ia-4 sublimes at 80 to 90 C. at 10.sup.2 mbar, its melting point is 193 C.

(15) FIG. 4 shows the thermogravimetric analysis data of Ia-4. The residual mass at 500 C. is 30%.

Example 5

(16) ##STR00008##

(17) Compound Ic-1 was synthesized according to Burckett-St. Laurent et al. in the Journal of the Chemical Society, Chemical Communications 1981, page 1141-1143. It is purely sublimable due to its waxy, oily nature.

(18) FIG. 5 shows the thermogravimetric analysis data of Ic-1. The residual mass at 500 C. is 39%.

Example 6

(19) ##STR00009##

(20) Compound Ib-4 was synthesized according to Organometallics volume 16 (1997), page 2049. The obtained compound is an orange-brown oil.

(21) FIG. 6 shows the thermogravimetric analysis data of Ib-4. The residual mass at 500 C. is 11.58%.