Hard laminated film, method of manufacturing the same and film-forming device

• US 8,197,647 B2
• Filed: 05/31/2007
• Issued: 06/12/2012
• Est. Priority Date: 02/02/2004
• Status: Active Grant

• Current Assignee: Kobe Steel Limited
• Original Assignee: Kobe Steel Limited
• Inventors: Yamamoto, Kenji, Kujime, Susumu, Takahara, Kazuki, Fujii, Hirofumi
• Primary Examiner(s): Hendricks, Keith
• Assistant Examiner(s): BRAYTON, JOHN JOSEPH
• Application Number:
  US11/756,014
• Publication Number:
  US 20070278090A1
• Time in Patent Office: 1,839 Days
• Field of Search: 204/298.41, 204/298.19, 204/298.2, 204/298.12, 204/192.16, 204/192.38, 204/192.15
• US Class Current: 204/192.15
• CPC Class Codes: C23C 14/0036 Reactive sputtering
• CPC Class Codes: C23C 14/0063 characterised by means for introducing or removing gases
• CPC Class Codes: C23C 14/06 characterised by the coating material C23C14/0021 , C23C14/04 take precedence
• CPC Class Codes: C23C 14/0641 Nitrides C23C14/0617 takes precedence
• CPC Class Codes: C23C 14/0647 Boron nitride
• CPC Class Codes: C23C 14/0652 Silicon nitride
• CPC Class Codes: C23C 14/0664 Carbonitrides
• CPC Class Codes: C23C 14/0676 Oxynitrides
• CPC Class Codes: C23C 14/16 on metallic substrates or on substrates of boron or silicon
• CPC Class Codes: C23C 14/22 characterised by the process of coating
• CPC Class Codes: C23C 14/325 Electric arc evaporation
• CPC Class Codes: C23C 14/35 by application of a magnetic field, e.g. magnetron sputtering C23C14/3457 takes precedence
• CPC Class Codes: C23C 14/568 Transferring the substrates through a series of coating stations C23C14/562 takes precedence
• CPC Class Codes: C23C 28/044 coatings specially adapted for cutting tools or wear applications
• CPC Class Codes: C23C 28/322 only coatings of metal elements only
• CPC Class Codes: C23C 28/34 including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
• CPC Class Codes: C23C 28/341 with at least one carbide layer
• CPC Class Codes: C23C 28/347 with layers adapted for cutting tools or wear applications
• CPC Class Codes: C23C 28/42 characterized by the composition of the alternating layers
• CPC Class Codes: C23C 28/44 characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness
• CPC Class Codes: C23C 30/00 : Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process C23C26/00, C23C28/00 take precedence
• CPC Class Codes: Y10T 428/24942 : including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/24975 : No layer or component greater than 5 mils thick
• CPC Class Codes: Y10T 428/26 : Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Abstract

A hard laminated Mm wherein a layer A and a layer B having specific compositions are deposited alternately so that the compositions of layer A and layer B are different. The thickness of layer A per layer is twice or more the thickness of layer B per layer, the thickness of layer B per layer is 5 nm or more, and the thickness of layer A per layer is 200 nm or less.

Claims

1. A method of forming a hard laminated film comprising a layer A and a layer B of specific compositions deposited alternately, wherein the crystal structure of layer A differs from the crystal structure of layer B, the thickness of layer A per layer is two or more times that of layer B per layer, the thickness of layer B per layer is 0.5 nm or more, and the thickness of layer A per layer is 200 nm or less,

wherein an arc vaporization source and a sputter vaporization source are simultaneously operated in a film-forming atmosphere comprising a reactive gas using a film-forming device comprising one or more of each of an arc vaporization source and sputter vaporization source also having a magnetic field applying function in the same vacuum container so that the components of said layer A are vaporized by the arc vaporization source and the components of said layer B are vaporized by the sputter vaporization source, respectively, and a substrate is moved relative to said vaporization sources so that said layer A and said layer B are deposited alternately on the substrate.

2. The method according to claim 1, wherein said film-forming atmosphere is a gaseous mixture of said reactive gas with an inert gas for sputtering, the partial pressure of said reactive gas being 0.5 Pa or more.

3. The method of forming a hard laminated film according to claim 1, wherein a hard film containing nitrogen is formed, and nitrogen is mixed with a sputter gas so that the partial pressure of the mixed nitrogen is 0.5 Pa or more.

4. The method according to claim 1, wherein the hard laminated film has, as its structure, one or more layer A/layer B/layer A/layer B units, and wherein the composition of each layer A may be the same or different, and the composition of each layer B may be the same or different.

5. The method according to claim 1, wherein the hard laminated film has, as its structure, one or more layer A/layer A/layer B/layer B units, one or more layer A/layer B/layer B/layer A units, one or more layer B/layer B/layer A/layer A units, or one or more layer B/layer A/layer A/layer B units, and wherein the composition of each layer A may be the same or different, and the composition of each layer B may be the same or different.

6. The method according to claim 1, wherein

Layer A:

(Cr<sub>1−

α</sub>

X<sub>α

) (Ba</sub>C_bN<sub>1−

a−

b−

c</sub>O_c)_e, wherein X is at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al and Si, and 0≦

α

≦

0.9, 0≦

a≦

0.15, 0≦

b≦

0.3, 0≦

c≦

0.1, 0.2≦

e≦

1.1 (α

is the atomic ratio of X, and a, b, c are respectively the atomic ratios of B, C, O),

and

Layer B;

B<sub>1−

s−

t</sub>C_sN_t, wherein 0≦

s≦

0.25, (1−

s−

t)/t≦

1.5 (s, t are respectively the atomic ratios of C and N), or

Si<sub>1−

x−

y</sub>C_xN_y, wherein 0<

x≦

0.25, 0.5≦

(1−

x−

y)/y≦

1.4 (x, y are respectively the atomic ratios of C and N), or

C<sub>1−

u</sub>N_u, wherein 0≦

u≦

0.6 (u is the atomic ratio of N).

7. The method according to claim 6, wherein α

is 0.

8. The method according to claim 6, wherein α

is 0.05≦

α

≦

0.9.

9. The method according to claim 6, wherein the hard laminated film has at least one of the half-value widths of the diffraction lines from the (111) plane and the (200) plane observed by an X-ray diffraction pattern obtained by the θ

-2θ

method using the CuKα

line, is 0.3°

or more.

10. The method according to claim 1, wherein

layer A:

(Ti<sub>1−

x−

y</sub>A1_xM_y)(B_aC_bN<sub>1−

a−

b−

c</sub>O_c), wherein x, y, a, b, c are respectively atomic ratios, 0.4≦

x≦

0.8, 0≦

y≦

0.6, 0≦

a≦

0.15, 0≦

b≦

0.3, 0≦

c≦

0.1, and M is one or more metal elements selected from the group consisting of 4A, 5A, 6A and Si, and

layer B;

B<sub>1−

x−

y</sub>C_xN_y, wherein x, y are respectively atomic ratios, 0≦

x≦

0.25 and B/N≦

1.5, or

Si<sub>1−

x−

y</sub>C_xN_y, wherein x, y are respectively atomic ratios, 0≦

x≦

0.25 and 0.5≦

Si/N≦

2.0, or

C<sub>1−

x</sub>N_x, wherein, x is an atomic ratio and 0≦

x≦

0.6, or

Cu<sub>1−

y</sub>(C_xN<sub>1−

x</sub>)_y, wherein x, y are respectively atomic ratios, 0≦

x≦

0.1 and 0≦

y≦

0.5.

11. The method according to claim 10, wherein said layer A has the composition (Ti₁₋

x−

yAl_xM_y)(B_aC_bN<sub>1−

a−

b−

c</sub>O_c), wherein, x, y, a, b, c are respectively atomic ratios, 0.5≦

x≦

0.8, 0.05≦

y≦

0.6, 0≦

a≦

0.15, 0≦

b≦

0.3, 0≦

c≦

0.1, and M is one or more metal elements selected from the group consisting of Cr, V, and Si.

12. The method according to claim 1, wherein the substrate is rotated so that it alternately passes in front of the arc vaporization sources and the sputter vaporization sources.

13. The method according to claim 1, wherein the substrate passes between arc vaporization sources and the sputter vaporization sources arranged in series.