JP2715834B2 - Dimethyl gold β-imino ketone for CVD - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for depositing gold by a CVD method, and more particularly to a material suitable for a laser CVD method. The gold thin film has characteristics such as electrical properties, optical properties, thermal stability, chemical stability, affinity with the substrate, etc.
It is used as a material for mirrors of optical elements. The present invention relates to a material for forming such a gold thin film by a CVD method, particularly a laser CVD method.

[0002]

2. Description of the Related Art To achieve the above object, dimethyl acetylacetonate gold (III) Me ₂ Au has conventionally been used.
Gold dimethyl β- such as (AcAc), Me ₂ Au (HFA)
A diketone complex has been used as a direct drawing vaporizable material for forming a gold thin film pattern by CVD due to its high vapor pressure. Although relatively sharp writing can be performed by the laser CVD method, the problem of bleeding (diffusion) of the line formed by the laser CVD method is unavoidable. As the demand for higher precision of laser formed patterns increases, this bleeding becomes even more problematic, and the development of materials with high pyrolysis temperature, which is the threshold value for pyrolysis, and sufficient photodegradability to improve pattern accuracy. Is required.

[0003]

Means for Solving the Problems The present inventor searched the literature, and as a result of examining the gold β-iminoketone complex described in Ser. Khim. Nauk., (5), 145 (1988), This material has proven to be very suitable for laser CVD materials.

[0004]

DETAILED DESCRIPTION OF THE INVENTION

Embedded image (Wherein Me is a methyl group and R ¹ and R ² are lower alkyl groups or phenyl groups, which may be the same or different). The material of the invention is particularly suitable for laser CVD, but naturally
Can also be used for Method D. Dimethyl gold (II) used in the present invention
I) The β-imino ketone complex can be synthesized by a method similar to a conventional gold β-diketone complex. In order to form a gold film using the dimethyl gold (III) β-imino ketone complex according to the present invention, the substrate is kept at 70 ° C. or less under a reduced pressure of 2 torr or less using a known laser CVD method. The complex was subjected to argon, helium, nitrogen,
It flows as a single component or a mixed gas of an inert gas such as hydrogen, and the flow rate is about 1 to 50 sccm.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described below in detail with reference to examples.

[Synthesis Example 1] [Synthesis of dimethyl (4-amino-3-pentene-2-onato) gold (III)] (1) Synthesis of dimethylgold (III) hydroxy complex Di-μ-iodotetramethyldiodium (III) ) ([(CH ₃ ) ₂ A
ul] ₂₎ was dissolved 5.00g in n- pentane in 150 ml, HNO ₃ of 0.001N containing AgNO ₃ of 3.18g
The aqueous solution was added dropwise and reacted. The organic layer was removed with vigorous stirring, and the formed precipitate of silver iodide was removed by filtration. 11 g of NaOH was added to the filtrate, and the mixture was stirred vigorously for 30 minutes. The generated silver oxide was removed by filtration to prepare an aqueous solution of a dimethylgold (III) hydroxy complex. (2) Synthesis of dimethyl (4-amino-3-pentene-2-onato) gold (III) In an aqueous solution of the dimethylgold (III) hydroxy complex of (1).
80 g of 4-amino-3-penten-2-one (commercially available)
A white precipitate was formed when 10 ml of an ethanol solvent containing (using Dojindo Laboratories reagents) was added. The crystals are taken out by filtration and purified by sublimation (107
C./0.15 torr), 3.90 g of dimethyl (4-amino-3-pentene-2-onato) gold (III) were obtained. 63.8 ° C. Decomposition temperature 179.7 ° C. ¹ H-NMR (CDC
L ₃ ): δ 0.88 ppm (singlet 3H), 0.93
(Singlet 3H), 2.00 (triplet 6H), 4.
90 (doublet 1H), 6.40 (singlet 3H).
1R absorption spectrum (KBr pellet): 3270, 2
975, 2900, 1597, 1555, 1530, 1
465, 1530, 1465, 1381, 1249, 1
215, 1205, 1191, 1020, 932, 85
5, 780, 700, 650, 623, 592, 58
5,460,432. MS: 325, 295, 280,
253, 238, 211, 225, 197. UV absorption spectrum: 312.4 nm (λmax)

[0006]

Synthesis Example 2 [Dimethyl (1-phenyl-3-amino-2-butene-
Synthesis of 1-onato) gold (III)] (1) Synthesis of 1-phenyl-3-amino-2-buten-1-one 1-phenyl-1,3-butanedione (commercially available (Tokyo Kasei) reagent as it is) 10.0 g was refluxed for 3 hours in a concentrated aqueous ammonia solution, and after cooling, the deposited precipitate was taken out by filtration and extracted with 1-phenyl-3-amino-2-butene-.
8.20 g of 1-one crystal was obtained. mp 143 ° C. (2) Synthesis of dimethyl (1-phenyl-3-amino-2-butene-1-onato) gold (III) 1-phenyl synthesized in (1) in an aqueous solution of dimethylgold (III) hydroxy complex of Synthesis Example 1 10 ml of an ethanol solution containing 2.40 g of -3-amino-2-buten-1-one
Was added slowly and a precipitate formed. The crystals are taken out by filtration and purified by sublimation (107 ° C./0.5° C.).
15 torr), dimethyl (1-phenyl-3-amino-2)
-Butene-1-onato) gold (III) 3.90 g was obtained.
mp 51.3 ° C, decomposition temperature 193.2 ° C.

[0007]

Comparative Example As a comparative example for the effect of the complex of the present invention,
A gold thin film was formed by thermal CVD and laser CVD using Me ₂ Au (AcAc). The silicon substrate was placed in a vacuum vessel having a quartz window and a heating means, and Me ₂ A
u (AcAc) was introduced into the above reaction vessel at a vaporization temperature of 60 ° C. under a reduced pressure of 2 torr with Ar at a flow rate of 10 sccm as a carrier gas. Keep the substrate at the temperature shown in Table 1,
Excimer laser light was irradiated on the substrate vertically from the quartz window at a repetition rate of 20 Hz, or gold was deposited on the substrate without irradiation. The film formation time at this time was 30 minutes. Laser irradiation conditions, purity of the formed film (EP
The results are shown in Table 1.

[0008]

Example 1 Dimethyl (4-amino-3-pentene-2-onato) gold (III) of Synthesis Example 1 (Me ₂ Au (KA)
Using A)), a gold thin film was formed by thermal CVD. A silicon substrate is placed in a vacuum vessel having a quartz window and a heating means, and Me ₂ Au (KAA) is vaporized at 80 ° C. and 100 ° C.
Ar at a flow rate of 10 sccm was introduced as a carrier gas into the above reaction vessel under a reduced pressure of 2 ° C. and a pressure of 2 torr. Table 2
The complex was thermally decomposed while keeping the temperature described in (1) to deposit gold on the substrate. The film formation time at this time was 30 minutes. Table 2 shows the experimental conditions and the purity of the formed film (by EPMA).

[0009]

Table 1 Results of heat and laser CVD test of Me ₂ Au (AcAc) No. Vaporization conditions Substrate temperature Laser laser power density Au content (wt%) 160 ° C 150 ° C None> 98 2 60 ° C 200 ° C None> 98 3 60 ° C 250 ° C None 97 4 60 ° C 300 ° C None 97 5 60 ° C 350 ° C None 98 6 60 ° C 400 ° C None 97 7 60 ° C 60 ° C XeCl 1.3W / cm ² > 98 8 60 ° C 150 ° C XeCl 1.3W / cm ² > 98

[0010]

Table 2 Results of thermal CVD test of Me ₂ Au (KAA) No. Vaporization conditions Substrate temperature Laser laser power density Au content (wt%) 1 80 ° C 200 ° C None Very thin film 2 80 ° C 250 ° C None 95.1 380 ℃ 350 ℃ None 98.6 4 100 ℃ 250 ℃ None ＞ 98 5 100 ℃ 300 ℃ None 97.5

[0011]

Example 2 Dimethyl (4-amino-3-pentene-2-onato) gold (III) of Synthesis Example 1 (Me ₂ Au (KA)
Using A)), a gold thin film was formed by thermal CVD. A silicon substrate was placed in a vacuum vessel having a quartz window and a heating means, and Me ₂ Au (KAA) was introduced into the above-mentioned reaction vessel as a carrier gas at a vaporization temperature of 80 ° C. under a reduced pressure of 2 torr under a flow rate of 10 sccm as Ar. . The substrate was maintained at the temperature shown in Table 3, and irradiated with an excimer laser beam perpendicularly to the substrate from a quartz window at a repetition rate of 20 Hz to photodecompose the complex and deposit gold on the substrate. The deposition time at this time is 3
0 minutes. Table 3 shows the laser irradiation conditions and the purity of the formed film (according to EPMA).

[0012]

[Table 3] Laser CVD test result of Me ₂ Au (KAA) No. Vaporization condition Substrate temperature Laser laser power density Au content (wt%) 1 80 ° C 80 ° C XeCl 1.3W / cm ² 98 2 80 ° C 150 ° C XeCl 1.3W / cm ² 97 3 80 ℃ 200 ℃ XeCl 1.3W / cm ² Thin film

[0013]

Example 3 Dimethyl (1-phenyl-3-) of Synthesis Example 2
Amino-2-butene-1-onato) gold (III) (Me ₂
Au (KBA)) was used to form a gold thin film by thermal CVD. A silicon substrate is placed in a vacuum vessel having a quartz window and a heating means, and Me ₂ Au (KBA) is vaporized at a temperature of 12 ° C.
Ar at a flow rate of 10 sccm was introduced as a carrier gas into the reaction vessel at 0 ° C. and 150 ° C. under a reduced pressure of 2 torr. The substrate was kept at the temperature shown in Table 4 to thermally decompose the complex,
Gold was deposited on the substrate. The film formation time at this time was 30 minutes. Experimental conditions and purity of the formed film (EPM
A) is shown in Table 4.

[0014]

Table 4 Results of thermal CVD test of Me ₂ Au (KBA) No. Vaporization conditions Substrate temperature Laser laser power density Au content (wt%) 1 120 ° C 200 ° C None Thin film 2 120 ° C 250 ° C None 96 3 120 ° C 350 ℃ None> 98 4 120 ℃ 300 ℃ None> 98 5 150 ℃ 300 ℃ None 97.5

[0015]

Example 4 The dimethyl (1-phenyl-3-
Amino-2-butene-1-onato) gold (III) (Me ₂ A)
u (KBA)) to form a gold thin film by laser CVD. A silicon substrate is placed in a vacuum container having a quartz window and a heating means, and Me ₂ Au (KBA) is vaporized at a temperature of 1
Ar at a flow rate of 10 sccm was introduced as a carrier gas into the reaction vessel at 50 ° C. under a reduced pressure of 2 torr. The substrate was maintained at the temperature shown in Table 5 and excimer laser light was irradiated at 20 Hz.
The complex was photodecomposed by vertically irradiating the substrate from the quartz window at the repetition number of times to deposit gold on the substrate. The film formation time at this time was 30 minutes. Table 5 shows the laser irradiation conditions and the purity of the formed film (according to EPMA).

[0016]

Table 5 Results of laser CVD test of Me ₂ Au (KBA) No. Vaporization conditions Substrate temperature Laser laser power density Au content (wt%) 1 150 ° C 100 ° C XeCl 1.3W / cm ² 98 2 150 ° C 150 ° C XeCl 1.3W / cm ² 97 3 150 ℃ 200 ℃ XeCl 1.3W / cm ² 96

[0017]

Since the substance used in the present invention has sublimability and a high decomposition temperature, it is particularly suitable for the laser CVD method. Known Me ₂ Au (AcAc), Me ₂ Au (TFA),
Compared to a dimethyl gold β-diketone complex such as Me ₂ Au (HFA), it has better decomposition characteristics with respect to excimer laser light such as XeCl, KrF 2 and ArF, so that it is advantageous for film formation by laser.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masayuki 1-297 Kitabukurocho, Omiya City, Saitama Prefecture Mitsui Materials Corporation Central Research Laboratory (72) Katsumi Ogi 1-297 Kitabukurocho, Omiya City, Saitama Prefecture Central Research Laboratory, Mitsubishi Materials Corporation (56) Reference IZV. SIB. OTD. AKAD. NAUK SSSR, SER. KHI M. NAUK, 1988, (5), 145-149

Claims (1)

(57) [Claims] [Claim 1] (Wherein Me is a methyl group and R ¹ and R ² are lower alkyl groups or phenyl groups, which may be the same or different).