Composition for forming porous film, porous film and method for forming the same, interlevel insulator film, and semiconductor device

• US 20040216641A1
• Filed: 11/12/2003
• Published: 11/04/2004
• Est. Priority Date: 11/13/2002
• Status: Abandoned Application

• Current Assignee: Panasonic Corporation (Panasonic Holdings Corporation)
• Original Assignee: Matsushita Electric Industrial Company Limited (Panasonic Holdings Corporation)
• Inventors: Nakagawa, Hideo, Sasago, Masaru, Hamada, Yoshitaka, Yagihashi, Fujio
• Application Number:
  US10/706,600
• Publication Number:
  US 20040216641A1
• Time in Patent Office: Days
• US Class Current: 106/287.16
• CPC Class Codes: C08G 77/04 Polysiloxanes
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09D 183/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C09D183/10 takes precedence
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/02203 the layer being porous
• CPC Class Codes: H01L 21/02216 the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/31695 Deposition of porous oxides or porous glassy oxides or oxide based porous glass
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Provided are a composition for forming film which can form a porous film excelling in dielectric constant, adhesiveness, uniformity of the film, mechanical strength and having low hygroscopicity; the prous film and the method for manufacturing the same, and a high-performing and highly reliable semiconductor device comprising the porous film inside. More specifically, provided is a composition for forming porous film obtainable by hydrolysis and condensation, in an acidic or alkaline condition, of a mixture of 100 parts by weight of one or more compounds selected of the group consisting of hydrolysable silicon compounds represented by Formulas (1) and (2) and partially hydrolyzed and condensed products of the hydrolysable silicon compounds represented by Formulas (1) and (2), and 0.1 to 20 parts by weight of one or more cross-linking agents selected from the group consisting of structure-controlled cyclic or multi-branched oligomers represented by Formulas (3) to (8).

R¹_aSiZ¹_4-a  (1)

R²_b(Z²)_3-bSi—Y—Si (R³)_cZ³_3-c  (2)

[R⁴(H) SiO]_e[R⁵(Z⁴) SiO]_f  (3)

(R⁶SiO_3/2)_g [R⁷(H) SiO]_h[R⁸(Z⁵)SiO]_i  (4)

(HSiO_3/2)_j(Z⁶SiO_3/2)_k  (5)

[H(Me)₂SiO_1/2]_L[Z⁷(Me)₂SiO_1/2]_m(R⁹SiO_3/2)_n[R¹⁰(Z⁸)SiO]_o  (6)

 [H (Me)₂SiO_1/2)]_p[Z⁹(Me)₂SiO_1/2]_q(SiO₂)_r(Z¹⁰SiO_3/2)_s  (7)

(Z¹¹₃SiO_1/2)_t(R¹¹₂SiO)_u(R¹²SiO_3/2)_v[R¹³(Z¹²) SiO]_w(SiO₂)_x(Z¹³SiO_3/2)y  (8)

Claims

1. A composition for forming porous film obtainable by hydrolysis and condensation, in an acidic or alkaline condition, of a mixture of parts by weight of one or more compounds selected of the group consisting of hydrolysable silicon compounds represented by Formulas (1) and (2) and partially hydrolyzed and condensed products of the hydrolysable silicon compounds represented by Formulas (1) and (2):

R¹_aSiZ¹_4-a 

 

(1)R²_b(Z²)_3-bSi—

y—

Si(R³)_cZ³_3-c 

 

(2)

wherein R1, R2 and R³ each independently represents a monovalent hydrocarbon group which may be substituted or non-substituted;

Z¹, Z² and Z³ each independently represents a hydrolysable group;

Y is independently selected from the group consisting of an oxygen atom, a phenylene group and an alkylene group having carbon atom number of 1 to 6;

a independently represents an integer of 0 to 3;

b and c each independently represents an integer of 0 to 2;

and 0.1 to 20 parts by weight of one or more cross-linking agents selected from the group consisting of structure-controlled cyclic or multi-branched oligomers represented by Formulas (3) to (8);

[R⁴(H)SiO]_e[R⁵(Z⁴)SiO]_f 

 

(3)(R⁶SiO_3/2)_g[R⁷(H)SiO]_h[R⁸(Z⁵)SiO]_i 

 

(4)(HSiO_3/2)_j(Z⁶SiO_3/2)_k 

 

(5)[H(Me)₂SiO_1/2]_L[Z⁷(Me)₂SiO1/2]_m(R⁹SiO_3/2)_n[R¹⁰(Z⁸)SiO]_o 

 

(6)[H(Me)₂SiO_1/2)]_p[Z⁹(Me)₂SiO_1/2]_q(SiO₂) _r(Z¹⁰SiO_3/2)_s 

 

(7)(Z¹¹₃SiO_1/2)_t(R¹¹₂SiO)_u(R¹²SiO_3/2)_v[R¹³Z(¹²)SiO]_w(SiO₂)_x(Z¹³SiO_3/2)_y 

 

(8)

wherein Me represents a methyl group;

R⁴ to R¹³ each independently represents a monovalent hydrocarbon group which may be substituted or non-substituted;

Z⁴ to Z¹³ each independently represents a hydrolysable group;

e, f, g, h, i, j and k each independently represents an integer of 0 to 10 with proviso that e+f≧

3, g+h+i≧

4 and j+k≧

4;

L, m, n, o, p, q, r, s, t, u, v, w, x and y each represents an integer of 0 to 20 with proviso that L+m+n+o≧

4, p+q+r+s≧

4 and t+u+v+w+x+y≧

3.

2. The composition for forming film according to claim 1 further comprising a solvent.

3. A method for forming porous film comprising a step of coating a substrate with said composition of claim 1 to form film and a step of forming pores in the film.

4. The method for forming porous film according to claim 3 wherein said step of forming pores comprise a first heating treatment at temperature high enough to evaporate the solvent in said film and a second heating treatment.

5. A porous film obtainable from said composition of claim 1.

6. An interlevel insulator film formable by said composition of claim 1.

7. A semiconductor device comprising internal porous film which is formable by a composition for forming porous film obtainable by hydrolysis and condensation, in an acidic or alkaline condition, of a mixture of parts by weight of one or more compounds selected of the group consisting of hydrolysable silicon compounds represented by Formulas (1) and (2) and partially hydrolyzed and condensed products of the hydrolysable silicon compounds represented by Formulas (1) and (2):

R¹_aSiZ¹_4-a  

 

(1)R²_b(Z²)_3-bS1-Y-S1(R³)_cZ³_3-c 

 

(2)

wherein R¹, R² and R³ each independently represents a monovalent hydrocarbon group which may be substituted or non-substituted;

Z¹, Z² and Z³ each independently represents a hydrolysable group;

Y is independently selected from the group consisting of an oxygen atom, a phenylene group and an alkylene group having carbon atom number of 1 to 6;

a independently represents an integer of 0 to 3;

b and c each independently represents an integer of 0 to 2;

and 0.1 to 20 parts by weight of one or more cross-linking agents selected from the group consisting of structure-controlled cyclic or multi-branched oligomers represented by Formulas (3) to (8);

[R⁴(H)SiO]_e[R⁵(Z⁴)SiO]_f 

 

(3)(R⁶SiO_3/2)_g[R⁷(H)SiO]_h[R⁸(Z⁵)SiO]_i 

 

(4)(HSiO_3/2)_j(Z⁶SiO_3/2)_k 

 

(5)[H(Me)₂SiO_1/2]_L[Z⁷(Me)₂SiO_1/2]_m(R⁹SiO_3/2)_n[R¹⁰(Z⁸)SiO]_o 

 

(6)(H(Me)₂SiO_1/2)]_p[Z⁹(Me)₂SiO_1/2]_q(SiO₂)_r(Z¹⁰SiO_3/2)_s 

 

(7)(Z¹¹₃SiO_1/2)_t(R¹¹₂SiO)_u(R¹²SiO_3/2)_v[R¹³(Z¹²)SiO]_w(SiO₂)(Z¹³SiO_3/2)_y 

 

(8)

wherein Me represents a methyl group;

R⁴ to R¹³ each independently represents a monovalent hydrocarbon group which may be substituted or non-substituted;

Z⁴ to Z¹³ each independently represents a hydrolysable group;

e, f, g, h, i, j and k each independently represents an integer of 0 to 10 with proviso that e+f≧

3, g+h+i≧

4 and j+k≧

4;

L, m, n, o, p, q, r, s, t, u, v, w, x and y each represents an integer of 0 to 20 with proviso that L+m+n+o≧

4, p+q+r+s>

4 and t+u+v+w+y≧

3.

8. The semiconductor device according to claim 7 wherein said porous film is between metal interconnections in a same layer of multi-level interconnections, or is between upper and lower metal interconnection layers.