JP2606066B2 - Dimethyl gold phosphonium complex for laser 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 laser CVD method. Gold thin films are used as electrode materials for semiconductor devices, photomask patterns, and mirror materials for optical devices because of their electrical, optical, thermal, chemical and affinity properties with substrates. It is used for The present invention uses such a gold thin film as a laser CV.
It relates to a material to be formed by the D method.

[0002]

2. Description of the Related Art Conventionally, Me ₂ A
dimethyl gold (I) such as u (AcAc) and Me ₂ Au (HFA)
II) β-diketone complexes have been used as vaporizable materials for direct writing of gold thin film patterns by laser CVD due to their high vapor pressure. In the laser CVD method, the substrate is usually heated for the purpose of assisting the fusion.
The problem of bleeding (diffusion) of the filaments formed by the method D 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 Chem. Ber., 11
0 , 3536 (1977) report some compounds as sublimable metal complexes. The present inventors picked up dimethyl (methanidebis (dimethylphosphonium methylide)) gold (III) and dimethyl (nitridebis (dimethylphosphoniummethylide)) gold (III) among them, which are excellent materials for producing gold films by laser CVD. Was confirmed.

[0004]

The present invention relates to a laser C comprising dimethyl (methanidebis (dimethylphosphonium methylide)) gold (III).
A gold film forming material by VD and a gold film forming material by laser CVD comprising dimethyl (nitridebis (dimethylphosphonium methylide)) gold (III) are provided.

Dimethyl (methanidebis (dimethylphosphonium methylide)) gold (III) (hereinafter sometimes referred to as compound I
Is written as

Embedded image 106 ° C, 115 ° C at 10 ^-4 torr
And decompose at 325 ° C.

Dimethyl (nitridebis (dimethylphosphonium methylide)) gold (III) (hereinafter sometimes referred to as compound II
Is written as

Embedded image Mp 155 ° C, 100 ° C at 10 ^-1 torr
And decompose at 268 ° C. These compounds can be prepared by the method described in the above-mentioned literature by using [(CH ₃ ) ₂ AuCl] ₂ and (CH ₃ ) ₃ P = C = P (CH ₃ ) ₃ or [(CH ₃ ) ₃ P
NP (CH ₃ ) ₃ ] Cl.

[0007]

Next, the present invention will be described in detail with reference to examples.

[0008]

Synthesis Example 1 2.61 g of [(CH ₃ ) ₂ AuCl] ₂ (5
Mmol) in about 100 ml of benzene and (CH ₃ ) ₃ P
= C = P (CH ₃ ) ₃ 3.28 g (20 mmol) was added and stirred at room temperature for 1 hour. By-product [(CH ₃ ) ₃ PCHP
(CH ₃ ) ₃ ] Cl precipitates.
Evaporation of the solvent gives crude compound I. This was purified by sublimation under reduced pressure to obtain 2.26 g of compound I. mp 104 ° C.

[0009]

Synthesis Example 2 2.61 g of [(CH ₃ ) ₂ AuCl] ₂ (5
Mmol) in about 100 ml of benzene and (CH ₃ ) ₃ P
3.48 g (20 mmol) of NP (CH ₃ ) ₂ CH ₂ were added,
Stir for 1 hour at room temperature. By-product [(CH ₃ ) ₃ PNP
(CH ₃ ) ₃ ] Cl precipitates.
Evaporation of the solvent gives crude compound II. This was purified by sublimation under reduced pressure to obtain 3.28 g of compound II. mp 152 ° C.

[0010]

Example 1 Using dimethyl (methanidebis (dimethylphosphonium methylide)) gold (III) of Synthesis Example 1, a gold thin film was formed by laser CVD. A silicon substrate is placed in a vacuum container having a quartz window and a heating means, and dimethyl (methanidebis (dimethylphosphonium methylide)) gold (III) is vaporized at a temperature of 80 ° C. to 120 ° C. and a pressure of 2 to.
Under a reduced pressure of rr, Ar at a flow rate of 10 sccm was introduced into the reaction vessel as a carrier gas. Keep the substrate at 100 ° C,
Excimer laser light was irradiated 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 film formation time at this time was 30 minutes. Laser irradiation conditions and the purity of the formed film (EP
MA) are shown in Table 1.

[0011]

[Table 1]

[0012]

Example 2 Using dimethyl (nitridebis (dimethylphosphonium methylide)) gold (III) of Synthesis Example 2,
It was formed a gold thin film at the laser CVD. Put the silicon substrate in a vacuum container having a quartz window and heating means,
Dimethyl (nitridobis (dimethylphosphonium methylide)) gold (III) was introduced into the above-mentioned reaction vessel at a vaporization temperature of 100 ° C. to 140 ° C. under a reduced pressure of 2 torr and Ar at a flow rate of 10 sccm as a carrier gas. 10 substrates
While maintaining the temperature at 0 ° C., the substrate was 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 2 shows the laser irradiation conditions and the purity of the formed film (according to EPMA).

[0013]

Table 2 Results of laser CVD test of dimethyl (nitridebis (dimethylphosphonium methylide)) gold (III) No. Vaporization conditions Substrate temperature Laser laser power density Au content (wt%) 1 100 ° C 100 ° C XeCl 1.3W / cm ² 98 2 120 ° C 100 ° C XeCl 1.3W / cm ² 98 3 140 ° C 100 ° C XeCl 1.3W / cm ² 96

[0014]

Since these substances have sublimability and a high decomposition temperature, they are suitable for laser CVD. Known Me ₂
Au (AcAc), Me ₂ Au (TFA), Me ₂ Au
Thermal decomposition temperature is higher than that of dimethyl gold (III) β-diketone complex such as (HFA), and it has good photodecomposition property for excimer laser light such as XeCl, KrF, ArF, etc. It is advantageous for formation.

 ──────────────────────────────────────────────────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 (56) References JP-A-64-11975 (JP, A) West German Patent Application Publication 2702326 (DE, A)

Claims (2)

(57) [Claims] 1. A gold film forming material by laser CVD comprising dimethyl (methanidobis (dimethylphosphonium methylide)) gold (III). 2. A material for forming a gold film by laser CVD comprising dimethyl (nitridebis (dimethylphosphonium methylide)) gold (III).