KR20190118976A - Wiring film and forming method of wiring film - Google Patents

Abstract

According to an aspect of the present invention, provided are a wiring film having excellent crystal orientation and a method for forming the wiring film simply and efficiently. According to an aspect of the present invention, a wiring film with a multilayer structure provided on a substrate comprises: an initial layer containing metal or alloy, or a compound thereof composed of a metal element having the film thickness of 3 to 200 nm deposited on the substrate; and second or more layers containing metal or alloy or a compound thereof composed of a metal element deposited on the initial layer, wherein an interface is provided between the initial layer and the second layer. In addition, the method forms, by sputtering under a vacuum atmosphere, a wiring film with a multilayer structure containing a metal element. The method comprises the steps of: performing vacuum exhaust after film formation of the initial layer having the thickness of 3 to 200 nm on the substrate; and performing film formation of the second or more layers on the initial layer.

Description

WIRING FILM AND FORMING METHOD OF WIRING FILM}

The present invention relates to a wiring film and a method for forming the wiring film.

In recent years, with the enlargement of the substrate used for display manufacture, it becomes difficult to maintain the quality of Al wiring film of a display including TFT (Thin Film Transistor) element. As an index of the quality of a metal wiring, in the case of Al wiring, the crystallinity and the orientation with respect to the Al (111) crystal surface are mentioned (nonpatent literature 1, 2).

In the case where a large substrate is used, uniform and rapid temperature control of the substrate and vacuum evacuation are difficult, and residual gas partial pressures such as moisture, oxygen, and nitrogen are increased, resulting in poor crystal orientation. When the residual gas partial pressure is high, since stacking defects occur in the crystal growth process, growth nuclei toward different orientations occur, and for example, Al (111) orientation is thought to be weakened. Especially as a method of improving orientation, it is important to remove the moisture which exists in the surface of a board | substrate (nonpatent literature 1, patent document 1).

Japanese Patent No. 3938437

Takashi Ito, VLSI Thin Film Technology, 1986 S. Vaidya, A. K. Sinha, Thin Solid Films, Volume 75, Issue 3, 16 January 1981, p.253-259

Generally as a method of removing the moisture of the surface of a board | substrate, the method of making the temperature of a board | substrate and the pressure in a vacuum chamber into suitable conditions is known. For example, when the temperature of the substrate is raised, degassing is promoted and moisture in the vicinity of the substrate surface is reduced. In addition, when the pressure in the vacuum chamber is lowered, gases such as moisture adsorbed on the substrate and in the atmosphere are reduced. As a result, since the factor which inhibits the movement of a metal atom is reduced, since the metal atom can be arranged most stably, the orientation of a crystal improves.

However, the relationship between these factors and the orientation is not fully elucidated, and it is not easy to select because it is necessary to clarify the optimum conditions experimentally. Moreover, even when the optimum conditions are found, these factors need to be within a certain range from the device configuration or the limitation of the tact, and there is a limit to the improvement.

In view of the above problems, the present invention provides a wiring film excellent in crystal orientation and a method for forming the wiring film simply and efficiently.

MEANS TO SOLVE THE PROBLEM The present inventors formed the metal element which is excellent in the orientation of a crystal | crystallization by forming an initial layer with a film thickness of 3-200 nm on a board | substrate by sputtering in a vacuum atmosphere, and forming a layer after 2nd layer on this initial layer. It was found that a wiring film having a multi-layer structure included was obtained, and the present invention was completed based on these findings.

That is, this invention is as follows.

1. A wiring film of a multilayer structure provided on a substrate,

An initial layer comprising a metal or an alloy composed of a metal element having a film thickness of 3 to 200 nm, or a compound thereof formed on the substrate;

A wiring film comprising a second or later layer comprising a metal or an alloy composed of a metal element formed on the initial layer or a compound thereof, and having an interface between the initial layer and the second layer.

2. The wiring film according to the above 1, wherein the main components of the initial layer and the second and subsequent layers are composed of the same metal, an alloy, or a compound thereof.

3. Said initial layer is oxygen atom containing layer, The wiring film as described in said 1 or 2 characterized by the above-mentioned.

4. Interlayer oxygen atom content rate is two or more, The wiring film as described in said 3 characterized by the above-mentioned.

5. Initial layer oxygen atom content rate is 0.02-1.5, The wiring film as described in said 4 characterized by the above-mentioned.

6. The metal element is Al, Cu, Ti, Mo, C, Si, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Zr, Nb, Ru, Rh, Pd, Ag The wiring film according to any one of the above 1 to 5, which is at least one selected from the group consisting of Cd, In, Sn, Sb, Te, Ta, W, Ir, Pt, Au, Pb, Ru, and Bi.

7. It is a wiring film of the multilayered structure containing a metal element provided on the board | substrate by sputtering in a vacuum atmosphere,

An initial layer having a film thickness of 3 to 200 nm deposited on the substrate;

And a second layer or later layer formed on the initial layer after evacuating after the deposition of the initial layer.

8. The wiring film according to the above 7, wherein the pressure after vacuum evacuation after film formation of the initial layer is 1.0 층 10 ⁻³ Pa or less.

9.Al, Cu, Ti, Mo, C, Si, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, The metals or alloys of at least one metal element selected from the group consisting of Sn, Sb, Te, Ta, W, Ir, Pt, Au, Pb, Ru, and Bi, or compounds thereof, as described in 7 or 8 above. Wiring film.

10. Said diffraction peak resulting from the specific crystal surface obtained by X-ray-diffraction whose ratio of the largest 1st diffraction peak and the next largest 2nd diffraction peak, and the 1st diffraction peak / 2nd diffraction peak is 5.0 or more said The wiring film in any one of 1-9.

11. Among the diffraction peaks resulting from the specific crystal plane obtained by X-ray diffraction with a film thickness of 200 nm or less, the ratio of the largest first diffraction peak to the next largest second diffraction peak, the first diffraction peak / agent The wiring film in any one of said 1-9 whose 2 diffraction peak is 2.3 or more.

12. Among the diffraction peaks resulting from the specific crystal plane obtained by X-ray diffraction, the ratio of the largest first diffraction peak to the next largest second diffraction peak and the first diffraction peak / second diffraction peak is determined by sputtering. The wiring film according to any one of 1 to 11, which is 5% or more larger than a wiring film formed of the same film thickness formed on the substrate and a single layer having the same composition as the initial layer.

13. The wiring film in any one of said 1-12 which has Al or Cu as a main component.

14. A wiring film containing Al as a main component, and the ratio of diffraction peaks due to Al (111) crystal planes obtained by X-ray diffraction and diffraction peaks due to Al (200) crystal planes, Al (111) / Al (200). ) Is 5.0 or more, and the wiring film according to 13 above.

15. A wiring film containing Al as a main component, the film thickness being 200 nm or less, and the ratio of diffraction peaks due to Al (111) crystal planes obtained by X-ray diffraction and diffraction peaks due to Al (200) crystal planes, Al The wiring film according to the above 13, wherein (111) / Al (200) is 2.3 or more.

16. The wiring according to the above-mentioned 13, wherein the wiring film having Al as a main component and whose half-value width (2θ) of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction measured by the following conditions is 0.38 ° or less. membrane.

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Tube voltage: 40㎸

Tube current: 40mA

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

17. The wiring film according to the above 13, wherein the wiring film has Al as a main component, and the distance between peaks when the rocking curve is measured at the position of the diffraction peak due to the Al (111) crystal plane is 15 ° or less.

14. A wiring film having a two-layer structure containing Al as a main component, and the ratio of the intensity of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction measured under the following conditions is 5.0 [ count / nm] or more].

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Tube voltage: 40㎸

Tube current: 40mA

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

19. The same film thickness formed on the substrate by sputtering at the half width (2θ) of the diffraction peak, which is a wiring film mainly composed of Al, and is caused by the Al (111) crystal plane obtained by X-ray diffraction. The wiring film according to the above 13, which is at least 5% smaller than the wiring film composed of a single layer having the same composition as the initial layer.

20. A wiring film containing Cu as a main component, and the ratio of diffraction peaks due to the Cu (111) crystal plane obtained by X-ray diffraction and diffraction peaks due to the Cu (200) crystal plane, Cu (111) / Cu (200). ) Is 5.0 or more, and the wiring film according to 13 above.

21. The wiring according to the above 13, wherein the wiring film having Cu as a main component and whose half value width (2θ) of the diffraction peak resulting from the Cu (111) crystal plane obtained by X-ray diffraction measured by the following conditions is 0.38 ° or less. membrane.

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Tube voltage: 40㎸

Tube current: 40mA

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

22. The same film thickness formed on the substrate by sputtering at the half width (2θ) of the diffraction peak which is a wiring film containing Cu as a main component and is attributable to the Cu (111) crystal plane obtained by X-ray diffraction. The wiring film according to the above 13, which is at least 5% smaller than the wiring film composed of a single layer having the same composition as the initial layer.

23. The wiring film according to any one of 1 to 22, wherein the substrate is a glass substrate, a silicon substrate, a quartz substrate, a resin substrate, a ceramic substrate, or a metal substrate.

24. A method of forming a wiring film of a multilayer structure containing a metal element by sputtering in a vacuum atmosphere,

Vacuum-exhaust after depositing an initial layer having a film thickness of 3 to 200 nm on the substrate, and

And depositing a layer after the second layer on the initial layer.

25. The method after vacuum exhaust pressure in after deposition of the initial layer described in 1.0Х10 ^-3 ㎩ or less, wherein 24.

26. The wiring film is Al, Cu, Ti, Mo, C, Si, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Zr, Nb, Ru, Rh, Pd, Ag, Composed of a metal or alloy of at least one metal element selected from the group consisting of Cd, In, Sn, Sb, Te, Ta, W, Ir, Pt, Au, Pb, Ru, and Bi, or a compound thereof Or the method described in 25.

27. Among the diffraction peaks attributable to the specific crystal plane obtained by X-ray diffraction, the wiring film has a ratio between the largest first diffraction peak and the next largest second diffraction peak, and the first diffraction peak / second diffraction peak. The method as described in any one of said 24-26 which is 5.0 or more.

28. The wiring film has a film thickness of 200 nm or less, and among the diffraction peaks resulting from the specific crystal plane obtained by X-ray diffraction, the ratio of the largest first diffraction peak to the next largest second diffraction peak, the first The method according to any one of the above 24 to 26, wherein the diffraction peak / second diffraction peak is 2.3 or more.

29. Among the diffraction peaks attributable to the specific crystal plane obtained by X-ray diffraction, the wiring film has a ratio between the largest first diffraction peak and the next largest second diffraction peak and the first diffraction peak / second diffraction peak. The method according to any one of 24 to 28, which is 5% or more larger than a wiring film formed of the same film thickness formed on the substrate by sputtering and a single layer having the same composition as the initial layer.

30. The method according to any one of 24 to 29, wherein the wiring film contains Al or Cu as a main component.

31. Said wiring film is a wiring film which has Al as a main component, and also the ratio of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction, and the diffraction peak resulting from the Al (200) crystal plane, Al (111). The method according to the above 30, wherein / Al (200) is 5.0 or more.

32. The said wiring film is a wiring film which has Al as a main component, the film thickness is 200 nm or less, and the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction, and the diffraction peak resulting from Al (200) crystal plane. The method according to the above 30, wherein the ratio Al (111) / Al (200) is 2.3 or more.

33. Said wiring film is wiring film which has Al as a main component, and the half value width (2 (theta)) of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction measured by the following conditions is 0.38 degrees or less, said The method as described in 30.

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Tube voltage: 40㎸

Tube current: 40mA

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

34. The method according to the above 30, wherein the wiring film is a wiring film containing Al as a main component, and the distance between peaks when the rocking curve is measured at the position of the diffraction peak due to the Al (111) crystal plane is 15 ° or less.

35. The wiring film is a wiring film having a two-layer structure containing Al as a main component, and the intensity of the diffraction peak and the film thickness of the two layers resulting from the Al (111) crystal plane obtained by X-ray diffraction measured according to the following conditions. The method according to the above 30, wherein the ratio is 5.0 [count / nm] or more.

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Tube voltage: 40㎸

Tube current: 40mA

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

36. The wiring film is a wiring film containing Al as a main component, and the half width (2θ) of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction is the same as that formed on the substrate by sputtering. The method according to the above 30, which is at least 5% smaller than a film thickness and a wiring film composed of a single layer having the same composition as the initial layer.

37. Said wiring film is a wiring film which has Cu as a main component, and is a ratio of the diffraction peak resulting from the Cu (111) crystal plane obtained by X-ray diffraction, and the diffraction peak resulting from the Cu (200) crystal plane, and Cu (111). The method according to the above 30, wherein / Cu (200) is 5.0 or more.

38. Said wiring film is a wiring film which has Cu as a main component, and the half value width (2 (theta)) of the diffraction peak resulting from the Cu (111) crystal plane obtained by X-ray diffraction measured by the following conditions is 0.38 degrees or less, The said The method as described in 30.

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Tube voltage: 40㎸

Tube current: 40mA

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

39. Said wiring film is a wiring film which has Cu as a main component, and the half value width (2theta) of the diffraction peak resulting from the Cu (111) crystal plane obtained by X-ray diffraction is the same as that formed on the said board | substrate by sputtering. The method according to the above 30, which is at least 5% smaller than a film thickness and a wiring film composed of a single layer having the same composition as the initial layer.

40. The method according to any one of 24 to 39, wherein the substrate is a glass substrate, a silicon substrate, a quartz substrate, a resin substrate, a ceramic substrate, or a metal substrate.

In the wiring film of the present invention, the orientation of crystals is remarkably improved. Further, according to the method of the present invention, after forming an initial layer having a specific thickness on a substrate, a second layer or later is formed on the initial layer, and an initial layer is formed by forming a wiring film composed of a multilayer structure film. The water molecules on the substrate can be remarkably removed at the time of sputtering, so that a wiring film with significantly improved crystal orientation can be formed simply and efficiently without being concerned with the method of controlling the temperature of the substrate or reducing the pressure for a long time. .

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing for demonstrating the 1st example of the sputtering apparatus used for the method of 1 aspect of this invention.
2 (a) to 2 (e) are cross-sectional views for explaining an example of a step of forming a wiring film of one embodiment of the present invention.
3 is a cross-sectional view for explaining an example of a liquid crystal display device having a wiring film of one embodiment of the present invention.
4 is a cross-sectional view for illustrating a second example of the sputtering apparatus used in the method of one embodiment of the present invention.
5 is a cross-sectional view for illustrating a third example of the sputtering apparatus used in the method of one embodiment of the present invention.
6 (a) to 6 (c) are schematic diagrams showing a process in which a wiring film is formed by normal single layer film formation. 6D to 6G are schematic diagrams showing a process of forming a wiring film having a two-layer structure by the method of one embodiment of the present invention.
(A) is a figure which observed the cross section of the film | membrane obtained by the comparative example 1-1 and Example 1-1 by SEM, and FIG. 7 (b) is implementation in FIG. It is an enlarged view of the cross section of the film | membrane obtained in Example 1-1.
FIG. 8A is a diagram in which the surface of the film obtained in Comparative Example 1-1 is observed by SEM, and FIG. 8B is a diagram in which the surface of the film obtained in Example 1-1 is observed by SEM. to be.
Fig. 9 is a diagram showing the results of depth direction analysis of the films obtained in Comparative Examples 1-5 and Example 1-7 from the Al film surface toward the glass side by XPS.
Fig. 10 shows the intensity of diffraction peaks resulting from the film thickness of the initial layer and the Al (111) crystal plane by X-ray diffraction of the obtained film in the film formed in two layers so that the total film thickness is 600 nm. Also referred to as Al (111) peak intensity] and a pressure after vacuum evacuation. The plot with a film thickness of 600 nm is shown here as a single layer.
FIG. 11 is a graph showing the relationship between the pressure after vacuum evacuation and the Al (111) peak intensity by X-ray diffraction of the obtained film in the film formed in two layers so that the total film thickness is 600 nm.
Fig. 12 shows the relationship between the film thickness of the initial layer, the Al (111) peak intensity by X-ray diffraction of the obtained film, and the pressure after vacuum evacuation in the film formed in two layers so that the total film thickness is 100 nm. It is a figure which shows. Plots having a film thickness of 100 nm indicate that they were monolayers.
FIG. 13 is a diagram showing the results of measuring the rocking curve of the Al (111) crystal plane with respect to the films obtained in Comparative Examples 1-1 and Example 1-1.

EMBODIMENT OF THE INVENTION Below, the wiring film of one aspect of this invention is demonstrated in detail. In this specification, "-" showing the numerical range is used in the meaning which includes the numerical value described before and after that as a lower limit and an upper limit, and unless otherwise specified, "-" uses the same meaning below. do.

[Wiring film]

The wiring film of the 1st aspect of this invention is a wiring film of the multilayered structure provided on the board | substrate,

An initial layer comprising a metal or an alloy composed of a metal element having a film thickness of 3 to 200 nm, or a compound thereof formed on the substrate;

It is a wiring film containing the 2nd layer or later layer containing the metal or alloy which consists of metal elements formed on the said initial layer, or its compound, The metal film which has an interface between an initial layer and a 2nd layer. to be. Here, the interface means that there is a boundary line where discoloration of the image becomes discontinuous between the initial layer and the second layer when the cross section is observed by the reflection electron image observation using SEM (Scanning Electron Microscopy). The difference in shade in the reflected electrons generally means a difference in composition, which means that there is a difference in crystal state, that is, a grain boundary at which crystal growth becomes discontinuous, and the second layer shows epitaxial growth. Presumably not, but not necessarily.

Moreover, although an interface is formed between an initial layer and a 2nd layer, even if an interface exists between other layers, it does not need to exist.

In the wiring film of the first aspect, the initial layer is an oxygen atom-containing layer and the interlayer oxygen atom content is 2 or more.

Here, the interlayer oxygen atom content ratio means a percentage value of the number of oxygen atoms in the initial layer obtained by measuring a depth direction profile using XPS (X-ray Photoelectron Spectroscopy) in a region from which the surface air oxide layer of the second and subsequent layers is removed. It is the value divided by the oxygen atom number percentage value.

The wiring film of a 1st aspect is characterized by the initial-layer oxygen atom content rate being 0.02-1.5.

Here, the initial layer oxygen atom content ratio is a value obtained by dividing the percentage of oxygen atoms in the initial layer by the percentage of metal atoms in the initial layer, which is obtained by measuring the depth direction profile using XPS.

In the initial layer, although hydrogen atoms accompanying water retention may exist, hydrogen atoms are not known by XPS, and thus, the oxygen atoms are detected as the oxygen atom detection amount as a value representing water retention.

The high interlayer oxygen atom content ratio and initial layer oxygen atom content ratio in the wiring film of the first aspect is such that the initial layer is formed while reacting with the moisture adhering to the substrate and / or causing the moisture to pop out by the sputter. Therefore, it is estimated that there is more moisture retention content than the 2nd layer formed into a film after glass surface moisture protrudes. Alternatively, since the sputter is stopped and evacuated once after the initial layer film formation, the surface may be oxidized by a small amount of water remaining in the space at that time, which may increase the amount of oxygen atoms. Even in the case of continuous film formation, a film is formed while reacting with the moisture adhering to the substrate and / or protruding the moisture by sputtering, but in this case, it is considered to be homogeneous because the moisture diffuses into the film. .

In addition, in the above consideration, although the possibility of the presence of oxygen which is not couple | bonded with hydrogen cannot be denied, this invention does not depend on the possibility.

Moreover, although XPS is suitable as a measurement of an interlayer oxygen atom content rate and an initial layer oxygen atom content rate, if the method can measure the atomic ratio of oxygen and metal in a film | membrane, a method is not limited to this. Other techniques include, for example, cross-sectional SEM-EDX (Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy), cross-sectional TEM-EDX (Transmission Electron Microscope-Energy Dispersive X-ray Spectroscopy), Auger Electron Spectroscopy, RBS (Rutherford Backscattering Spectrometry) ) And D-SIMS (Dynamic-Secondary Ion Mass Spectrometry).

In the cross-sectional analysis, the cross-sectional layer may be oxidized by air or the like during cross-sectional fabrication. Of course.

The wiring film of a 1st aspect contains the metal or alloy whose initial layer consists of a metal element, or its compound, Preferably it contains the metal or alloy consisting of a metal element. Moreover, the wiring film of 1st aspect of this invention contains the metal or alloy whose metal after 2nd layer consists of metal elements, or its compound, Preferably contains the metal or alloy consisting of metal elements. As a compound of a metal or an alloy, the oxide and nitride of a metal or an alloy are mentioned, for example.

The metal element is Al, Cu, Ti, Mo, C, Si, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Zr, Nb, Ru, Rh, Pd, Ag, Cd At least one selected from the group consisting of In, Sn, Sb, Te, Ta, W, Ir, Pt, Au, Pb, Ru, and Bi, Al, Cu, Ti, Mo are more preferable, Al or Cu is more preferred.

The wiring film of the 2nd aspect of this invention is a wiring film of the multilayer structure containing a metal element provided on the board | substrate by sputtering in a vacuum atmosphere,

An initial layer having a film thickness of 3 to 200 nm deposited on the substrate;

A wiring film including the second and subsequent layers formed on the initial layer after evacuating after the deposition of the initial layer.

As for the wiring film of a 2nd aspect, it is preferable that the pressure after vacuum evacuation after film-forming of an initial layer is 1.0Х10 <^-3> Pa or less, More preferably, it is 5.0Х10 <^-4> Pa or less, More preferably, it is 3.0Х10 <^-4> Pa It is as follows. The orientation of the crystal is improved by forming the wiring film after the second layer onto the initial layer after the pressure by the vacuum exhaust in after deposition of the initial layer to less than 1.0Х10 ^-3 ㎩.

The wiring film of the second aspect is Al, Cu, Ti, Mo, C, Si, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Zr, Nb, Ru, Rh, Pd, Ag , Cd, In, Sn, Sb, Te, Ta, W, Ir, Pt, Au, Pb, Ru and Bi is preferably composed of a metal or alloy of a metal element selected from the group consisting of, or a compound thereof It is more preferable that it is comprised with the metal or alloy of the metal element of Al, Cu, Ti, Mo, or its compound, and it is still more preferable to be comprised with the metal or alloy of the metal element of Al or Cu, or its compound.

It is preferable that the wiring film of a 2nd aspect contains the metal or alloy which consists of a metal element, or its compound, and, more preferably, contains the metal or alloy which consists of a metal element. Moreover, as for the wiring film of 2nd aspect of this invention, it is preferable that the 2nd layer or more layer contains the metal or alloy which consists of a metal element, or its compound, and it is more preferable that a metal or alloy is included.

The wiring film of a 1st aspect and a 2nd aspect may be the same composition, or a different composition may be sufficient as the initial layer and the layer after 2nd layer. In addition, although an initial layer and a 2nd layer or more may be the same or different main components, two layers can be processed with the same target, but productivity is based on the fact that several types of liquids are not needed for the etching performed after film-forming. It is preferable that the main components are the same from the point of improving.

It is preferable that the wiring film of a 1st aspect and a 2nd aspect has Al or Cu as a main component. In this invention, a main component means containing 50 atomic% or more of the element used as a main component. Therefore, "having Al as a main component" means "containing 50 atomic% or more of Al atoms". As for the wiring film of a 1st aspect and a 2nd aspect, it is more preferable to contain 75 atomic% or more of Al or Cu, It is still more preferable to contain 90 atomic% or more of Al or Cu, It is especially preferable that it consists of Al or Cu.

The film thickness of the initial layer in the wiring film of the 1st aspect and the 2nd aspect is 3-200 nm, Preferably it is 4-100 nm, More preferably, it is 5-50 nm, More preferably, it is 10- 30 nm. By setting the film thickness of the initial layer to 3 to 200 nm, a wiring film excellent in the crystal orientation is obtained.

It is preferable to adjust the film thickness of an initial layer according to the film thickness of a wiring film. Specifically, when the film thickness of the wiring film is 200 nm or less, the film thickness of the initial layer is preferably 3 nm or more, more preferably 5 nm or more, and still more preferably 10 nm or more. Moreover, it is preferable that the film thickness of an initial layer is 50% or less of the film thickness of a wiring film, More preferably, it is 30% or less, More preferably, it is 10% or less. By setting the film thickness of the initial layer to 3 nm or more of the film thickness of the wiring film and to 50% or less of the film thickness of the wiring film, a wiring film having excellent crystal orientation is obtained.

It is preferable that the film thickness of the 1st aspect and the 2nd aspect is 30-1000 nm, More preferably, it is 50-700 nm, More preferably, it is 100-400 nm. When the film thickness of the wiring film is 30 nm or more, the electrical resistance is prevented from rising due to the influence of the surface scattering of the electrons, and the film thickness of the second and subsequent layers of good quality is thickened, so that the film quality can be further improved. have. Moreover, when a film thickness is 1000 nm or less, while preventing a film from peeling easily from a board | substrate by a film stress, production efficiency can be improved.

As for the wiring film of a 1st aspect and a 2nd aspect, it is preferable that the total layer number of a multilayered structure is 2-10, More preferably, it is 2-5, More preferably, it is 2-4. By setting the total number of layers of the multilayer structure to 2 to 10, both the improvement of the film quality and the shortening of the tact according to the film forming process can be achieved.

It is preferable that the interlayer oxygen atom content ratio of the wiring film of a 1st aspect is two or more, More preferably, it is four or more. In addition, when oxygen is not contained in the layer after 2nd layer at all, the ratio of interlayer oxygen atom content may be infinite.

In addition, the wiring film of the first aspect preferably has an initial layer oxygen atom content ratio of 0.02 to 1.5, more preferably 0.02 to 0.5, still more preferably 0.02 to 0.3, and particularly preferably 0.03 to 0.15. Thereby, it can be set as the appropriate initial layer which can improve the crystal orientation after 2nd layer.

The wiring film of the 1st aspect and the 2nd aspect has the ratio of the largest diffraction peak and the next largest 2nd diffraction peak among the diffraction peaks resulting from the specific crystal surface obtained by X-ray diffraction, and the 1st diffraction peak / It is preferable that a 2nd diffraction peak is 5.0 or more, It is more preferable that it is 8.0 or more, It is further more preferable that it is 12.0 or more, It is especially preferable that it is 15.0 or more.

The wiring film of the 1st aspect and the 2nd aspect has a film thickness of 200 nm or less, and among the diffraction peaks resulting from the specific crystal surface obtained by X-ray diffraction, the largest first diffraction peak and the next largest second diffraction peak Ratio, the first diffraction peak / second diffraction peak is preferably 2.3 or more, more preferably 3.5 or more, and even more preferably 5.0 or more.

The wiring film of the 1st aspect and the 2nd aspect has the ratio of the largest diffraction peak and the next largest 2nd diffraction peak among the diffraction peaks resulting from the specific crystal surface obtained by X-ray diffraction, and the 1st diffraction peak / It is preferable that 2nd diffraction peak is 5% or more larger than the wiring film which consists of the same film thickness formed on the said board | substrate by sputtering, and a single layer which is the same composition as the said initial layer, It is more preferable that it is 10% or more larger More preferably 20% or more, and particularly preferably 40% or more.

The wiring film of the first aspect and the second aspect is a wiring film mainly composed of Al, and the ratio of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction and the diffraction peak resulting from the Al (200) crystal plane. It is preferable that Al (111) / Al (200) is 5.0 or more, More preferably, it is 10.0 or more, More preferably, it is 15.0 or more. When Al (111) / Al (200) is 5.0 or more, a wiring film with improved orientation is obtained. The upper limit of Al (111) / Al (200) is not particularly limited but is typically 50.0 or less.

The wiring film of the first aspect and the second aspect is a wiring film mainly composed of Al, having a film thickness of 200 nm or less, and a diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction and the Al (200) crystal plane. It is preferable that the ratio of the diffraction peak resulting from and Al (111) / Al (200) is 2.3 or more, More preferably, it is 3.5 or more, More preferably, it is 5.0 or more. When Al (111) / Al (200) is 2.3 or more, a wiring film with improved orientation is obtained. The upper limit of Al (111) / Al (200) is not particularly limited but is typically 50.0 or less.

The wiring film of the first and second aspects is a wiring film containing Al as a main component, and at a half width of a peak resulting from an Al (111) crystal plane obtained by X-ray diffraction whose crystallite size is measured according to the following conditions. When prescribed | regulated, it is preferable that the half value width (2theta) of the said diffraction peak is 0.38 degrees or less, More preferably, it is 0.36 degrees or less, More preferably, it is 0.34 degrees or less. When the half value width (theta) of the said diffraction peak is 0.38 degrees or less, the wiring film with the improved orientation is obtained. The lower limit of the half width (2θ) of the diffraction peak is not particularly limited but is typically 0.30 ° or more.

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Tube voltage: 40㎸

Tube current: 40mA

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

The wiring film of 1st aspect and 2nd aspect is a wiring film which has Al as a main component, It is preferable that the distance between the peaks of the rocking curve (ω scan) with respect to the Al (111) crystal plane is 15 degrees or less, More preferably, Is 12 [°] or less, More preferably, it is 9 [°] or less. When the said distance between peaks is 15 [degrees] or less, the orientation film | membrane of the crystal | crystallization is excellent and it becomes an orientation film which the dispersion | distribution (fluctuation and fluctuation) of a crystal axis reduced. The lower limit of the distance between the peaks is not particularly limited, but is typically 2 [°] or more.

In general, the strength of the orientation is often expressed by the half width of the rocking curve. However, in the wiring film of the first and second aspects, the rocking curve had two maximal points. The strength and weakness of the orientation were discussed by the distance between the peaks. The distance between the peaks of the rocking curve can be measured, for example, as follows. X-ray diffraction measurement is performed to fix 2θ at the position of the diffraction peak resulting from the Al (111) crystal plane (the position of 2θ = 38.5 ° formed by the incident X-ray direction and the diffraction X-ray direction), and the incident angle X-ray and the crystal surface In the diffraction intensity distribution (rocking curve) obtained by varying each of ω only and performing X-ray diffraction measurement, instead of the half width, this waveform was peak-fitted by a pseudo-Voight function to be a composite waveform of two acids. It is assumed that the distance between peaks of each mountain is used. It is preferable that the distance between the peaks of each acid is 15 [°] or less, more preferably 12 [°] or less, and still more preferably 9 [°] or less. The lower limit of the distance between the peaks is not particularly limited, but is typically 2 [°] or more.

The wiring film of the first aspect and the second aspect is a wiring film having a two-layer structure containing Al as a main component, and the intensity of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction measured according to the following conditions. It is preferable that the ratio of the film thickness of two layers is 5.0 [count / nm] or more, More preferably, it is 7.0 [count / nm] or more, More preferably, it is 10.0 [count / nm] or more. The upper limit of the ratio is not particularly limited, but is typically 30.0 [count / nm] or less.

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Tube voltage: 40㎸

Tube current: 40mA

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

The wiring film of the first and second aspects is a wiring film containing Al as a main component, and the half width (2θ) of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction is determined by sputtering. Compared with the wiring film which consists of the same film thickness formed on the phase and the single | mono layer which is the same composition as the said initial layer, it is preferable that it is 5% or more small, It is more preferable that it is 10% or more small, It is further more preferable that it is 15% or less small. By the said range, the wiring film in which the orientation of a crystal | crystallization was improved is obtained.

The wiring film of 1st aspect and 2nd aspect is a wiring film which has Cu as a main component, and also the ratio of the diffraction peak resulting from the Cu (111) crystal plane obtained by X-ray diffraction, and the diffraction peak resulting from Cu (200) crystal plane. It is preferable that Cu (111) / Cu (200) is 5.0 or more, More preferably, it is 5.5 or more, More preferably, it is 6.0 or more. When Cu (111) / Cu (200) is 5.0 or more, the wiring film with the improved orientation is obtained. The upper limit of Cu (111) / Cu (200) is not particularly limited but is typically 10.0 or less.

The wiring film of the 1st aspect and the 2nd aspect is a wiring film which has Cu as a main component, and also the half value width (2 (theta)) of the diffraction peak resulting from the Cu (111) crystal surface obtained by X-ray diffraction measured by the following conditions is It is preferable that it is 0.38 degrees or less, More preferably, it is 0.36 degrees or less, More preferably, it is 0.34 degrees or less. The lower limit of the half width (2θ) of the diffraction peak is not particularly limited but is typically 0.30 ° or more.

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Tube voltage: 40㎸

Tube current: 40mA

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

The wiring film of the 1st aspect and the 2nd aspect is a wiring film which has Cu as a main component, and the half value width (2 (theta)) of the diffraction peak resulting from the Cu (111) crystal plane obtained by X-ray diffraction produces the said board | substrate by sputtering. Compared with the wiring film which consists of the same film thickness formed on the phase and the single | mono layer which is the same composition as the said initial layer, it is preferable that it is 5% or more small, It is more preferable that it is 10% or more small, It is further more preferable that it is 15% or less small. By the said range, the wiring film in which the orientation of a crystal | crystallization was improved is obtained.

As for the wiring film of a 1st aspect and a 2nd aspect, it is preferable that a board | substrate is a glass substrate, a silicon substrate, a quartz substrate, a resin substrate, a ceramic substrate, or a metal substrate.

[Formation of wiring film]

A method of one embodiment of the present invention is a method of forming a wiring film having a multi-layer structure containing a metal element by sputtering in a vacuum atmosphere, and vacuum exhausting after forming an initial layer having a film thickness of 3 to 200 nm on the substrate. And a step of forming a layer after the second layer on the initial layer.

The code | symbol 1 of FIG. 1 shows the 1st example of the sputtering apparatus used for the method of 1 aspect of this invention. The sputtering apparatus 1 has the vacuum chamber 2, and the sputtering target 11 containing a metal element is arrange | positioned in the vacuum chamber 2.

The vacuum exhaust system 9 and the gas introduction system 8 are connected in the vacuum chamber 2. After holding the board | substrate 21 in the board | substrate holder 7, it conveys into the vacuum chamber 2, vacuum-exhausts the inside of the vacuum chamber 2 by the vacuum exhaust system 9, and makes it a vacuum atmosphere.

The sputtering target 11 is connected to a power source 5 disposed outside the vacuum chamber 2, and introduces a voltage from the power source 5 to the sputtering target 11 while introducing a sputtering gas from the gas introduction system 8. When applied, a plasma is formed near the surface of the sputtering target 11 and the sputtering target 11 is sputtered. Particles of the material constituting the sputtering target 11 are released to reach the surface of the substrate 21. As shown in (b), the initial layer 22 is formed.

The pressure in the initial layer 22, the vacuum chamber (2) at the time of formation of is usually 1.0Х10 ^-3 to ^-7 1.0Х10 ㎩, and preferably 5.0Х10 ^-4 to ^-6 1.0Х10 ㎩, more preferably Is 3.0Х10 ⁻⁴ to 1.0Х10 ⁻⁵ μs. In addition, the temperature in the vacuum chamber 2 at the time of formation of the initial layer 22 is 25-250 degreeC normally, Preferably it is 75-200 degreeC, More preferably, it is 100-150 degreeC.

When the film thickness of the initial layer 22 was formed to be 3 to 200 nm, voltage application and introduction of the sputter gas are stopped. After sputtering the sputtering target 11 in the vacuum chamber 2 after evacuating after forming the initial layer 22, the layer 23 after the 2nd layer is formed in the surface of the initial layer 22 (FIG. 2). (C)].

The pressure after vacuum evacuation after the formation of the initial layer 22 is preferably 1.0 1.010 ⁻³ Pa or lower, more preferably 5.0 10 10 ⁻⁴ Pa or lower, still more preferably 3.0 1010 ⁻⁴ Pa or lower. In this specification, the "pressure after vacuum evacuation after film formation of an initial layer" means the pressure before evacuating sputtering gas after vacuum evacuation after film formation of an initial layer, ie, just before forming a 2nd layer. Moreover, the temperature in the vacuum chamber 2 at the time of formation of the layer 23 after 2nd layer is 25-250 degreeC normally, Preferably it is 75-200 degreeC, More preferably, it is 100-150 degreeC.

The substrate 21 is carried out from the sputtering apparatus 1 when the layer 23 after the 2nd layer was formed in predetermined | prescribed film thickness. On the surface of the board | substrate 21, as shown in FIG.2 (c), the wiring film 24 which consists of the initial layer 22 and the layer 23 after the 2nd layer is formed.

Next, as shown in FIG. 2D, the patterned resist film 26 is disposed on the surface of the wiring film 24, and the wiring film 24 exposed on the bottom surface of the resist film 26 is disposed. When exposed to etching liquid or etching gas such as weak acid, the patterned wiring film 25 is formed as shown in Fig. 2E.

When the main components of the initial layer 22 and the second and subsequent layers 23 are the same, etching can be performed with etching liquids (or etching gases) of the same composition, so that the resist film can be newly placed when the initial layer 22 is etched. There is no need.

In the above example, the initial layer 22 and the second and subsequent layers 23 are formed in the vacuum chamber 2 of the same sputtering apparatus 1, but the present invention is not limited thereto. As shown to FIG. 4, 5 mentioned later, you may form the initial layer 22 and the layer 23 after the 2nd layer by sputtering each target in each vacuum chamber.

The said board | substrate 21 is a board | substrate used for the below-mentioned TFT board | substrate and a semiconductor device, For example, a glass substrate, a silicon board | substrate, a quartz board | substrate, a resin board | substrate, a ceramic board | substrate, a metal board | substrate, etc. are mentioned.

In addition, if the initial layer 22 and the second layer after the second layer 23 are continuously formed in the same sputtering apparatus 1, the initial layer 22 and the second layer after the second layer 23 are not exposed to the atmosphere. Can improve membrane quality.

Reference numeral 80 in FIG. 4 denotes the sputtering apparatus of the second example, and reference numeral 90 in FIG. 5 denotes the sputtering apparatus of the third example. The sputtering apparatuses 80 and 90 of the 2nd and 3rd examples are the 1st vacuum chamber 2a, the 2nd vacuum chamber 2b connected to the 1st vacuum chamber 2a, and the 1st vacuum chamber 2a. It has the 1st sputtering target 11a arrange | positioned inside and the 2nd sputtering target 11b arrange | positioned in the 2nd vacuum chamber 2b.

The process of forming the multilayer structure film for wiring films using the sputtering apparatus 80, 90 of a 2nd example and a 3rd example is demonstrated.

First, a vacuum atmosphere is formed inside the first and second vacuum chambers 2a and 2b by the vacuum exhaust system 9, and the substrate 21 is kept inside the first vacuum chamber 2a while maintaining the vacuum atmosphere. It carries in and is hold | maintained in the board | substrate holder 7a.

Sputtering gas is introduced into the first vacuum chamber 2a from the gas introduction system 8 while continuing the vacuum evacuation, and a voltage is applied from the power supply 5 to the first sputtering target 11a and the first sputtering target in a vacuum atmosphere. After sputtering 11a to form the initial layer 22, the introduction of the sputtering gas is stopped and vacuum evacuation is performed.

The sputtering apparatuses 80 and 90 of the second and third examples form different vacuum atmospheres in the respective vacuum chambers 2a to 2c. Therefore, as compared with the case in which different vacuum atmospheres are alternately formed in the same vacuum chamber 2 as in the sputtering apparatus 1 of the first example, a long time is required for evacuation from the completion of film formation of one film to the next film formation. Does not cost. In addition, since the initial layer and the second and subsequent layers can be formed in each vacuum chamber at the same time, productivity can be improved.

In addition, as in the sputtering apparatus 90 of the third example, the number of vacuum tanks 2a to 2c is the same as the number of layers having a multilayer structure constituting the wiring films 24 and 25, and each film is subjected to a dedicated vacuum tank 2a. When the film is formed in the second through 2c), the productivity can be improved.

The sputtering apparatus 80 of a 2nd example may directly connect the 1st, 2nd vacuum chamber 2a, 2b, as shown in FIG. 4, and conveys the 1st, 2nd vacuum chamber 2a, 2b the same. You may connect to a chamber and carry in and out the board | substrate 21 between the 1st, 2nd vacuum chamber 2a, 2b through the said transfer chamber.

In addition, the sputtering apparatus 90 of a 3rd example connects the 1st-3rd vacuum chambers 2a-2c in series, and connects the board | substrate 21 to the 2nd vacuum chamber 2b, as shown in FIG. You may convey to the 3rd vacuum chamber 2c from the 1st vacuum chamber 2a through. In addition, you may connect the 1st-3rd vacuum chambers 2a-2c to the same conveyance chamber, and carry-in / out the board | substrate 21 between the 1st-3rd vacuum chambers 2a-2c through this conveyance chamber.

In any case, since the board | substrate 21 moves between vacuum chambers without contacting air | atmosphere, the wiring films 24 and 25 with a favorable film quality are obtained.

The substrate 21 on which the initial layer 22 is formed is loaded into the second vacuum chamber 2b from the first vacuum chamber 2a and held in the substrate holder 7b. The sputtering gas is introduced while evacuating the inside of the second vacuum chamber 2a to sputter the second sputtering target 11b in a vacuum atmosphere to form a layer 23 after the second layer.

6 (a) to 6 (c) are schematic diagrams showing a process in which a wiring film is formed by normal single layer film formation. 6D to 6G are schematic diagrams showing a process of forming a wiring film having a two-layer structure by the method of one embodiment of the present invention.

As shown in FIGS. 6A and 6D, Si—OH groups and water molecules 17 exist in the vicinity of the surface of the substrate 21 before the treatment. As shown in Figs. 6 (b) to 6 (c), in the normal single layer film formation, when the target layer containing the metal element is sputtered to form the single layer 18 on the substrate 21, the sputtered metal atoms, The interaction between the Si-OH group and the adsorbed water molecules and the influence of the water molecules 17 near the substrate 21 protruding upon sputtering result in a wiring film having a lower crystal orientation.

In the method of one aspect of the present invention, after the initial layer 22 having a thickness of 3 to 200 nm is formed on the substrate 21 by sputtering in a vacuum atmosphere (FIGS. 6E to 6F). After the film formation is stopped and vacuum evacuation, the second and subsequent layers 23 are formed on the initial layer 22 to form the wiring film 24 (Fig. 6 (g)).

In the present invention, the water in the vicinity of the substrate surface is extremely removed by the sputter which forms the initial layer 22 (FIG. 6 (f)). It is thought that by forming into a film, the orientation of a crystal | crystallization improves and the quality wiring film 24 is obtained. Although such a hypothesis is considered as a reason for exerting the effect by the method of one aspect of this invention, this invention is not limited to this.

[Electronic device]

Next, with reference to FIG. 3, the liquid crystal display device as an example of the electronic device which has a wiring film of this invention is demonstrated. In FIG. 3, the liquid crystal display device 3 includes a TFT substrate 75 and a color filter substrate 95.

This liquid crystal display device 3 is of an active matrix type, and the TFT substrate 75 has a display pixel 80, a storage capacitor 84, and a TFT (thin film transistor) 85 on a glass substrate 76.

The storage capacitor 84 has a storage electrode 83, the display pixel 80 has a pixel electrode 81, and the TFT 85 has a gate electrode 86, a source electrode 87, and a drain electrode 88. Has The storage electrode 83, the gate electrode 86, the source electrode 87, and the drain electrode 88 are constituted by the wiring films 24 and 25.

The TFT 85 also includes a gate insulating film 89, a channel semiconductor layer 91, a source semiconductor layer 92, and a drain semiconductor layer 93.

A part of the surface of the drain electrode 88 is exposed and is in contact with the pixel electrode 81 extending from the display pixel 80. The pixel electrode 81 extends to a portion where the storage capacitor 84 is located, and is disposed to face the storage electrode 83 disposed on the glass substrate 76 with the insulating film (gate insulating film 89) therebetween. The storage capacity is formed by the opposing portions.

The gate electrode 86 and the gate insulating film 89 are disposed on one side of the channel semiconductor layer 91 between the source semiconductor layer 92 and the drain semiconductor layer 93. On the opposite side of the channel semiconductor layer 91, the source semiconductor layer 92 and the drain semiconductor layer 93 are spaced apart from each other.

The source electrode 87 and the drain electrode 88 are in contact with the surfaces of the drain semiconductor layer 93 and the source semiconductor layer 92, respectively. The gate electrode 86 and the source electrode 87 are configured to be led out of the TFT 85 so that a voltage from an external power source can be applied.

The TFT 85 and the color filter substrate 95 are provided at a predetermined distance, and the liquid crystal 49 is enclosed therebetween. In the color filter substrate 95, the black matrix 97 is disposed at a position facing the TFT 85, and the color filter 98 is disposed at a position facing the display pixel 80. The common electrode 100 is disposed in at least a portion of the color filter substrate 95 that faces the display pixel 80. The pixel electrode 81 and the common electrode 100 may be, for example, a transparent conductive film such as ITO.

The TFT substrate 75 includes a polarizing plate 94, and the color filter substrate 95 includes a polarizing plate 104. When a voltage is applied between the pixel electrode 81 and the common electrode 100 by the conduction and blocking of the TFT 85, the orientation of the liquid crystal 49 on the display pixel 80 is changed to pass through the liquid crystal 49. The deflection direction of the light is changed, and the blocking and transmission of light irradiated to the display pixel 80 to the outside of the liquid crystal display device 3 are controlled.

The storage electrode 83, the gate electrode 86, the source electrode 87, and the drain electrode 88 are composed of the wiring films 24 and 25 formed by the present invention, and the initial layer 22 is formed of a glass substrate ( 76 or in contact with the semiconductor layers 92 and 93.

The storage electrode 83 and the gate electrode 86 are in contact with the glass substrate 76, and the source electrode 87 and the drain electrode 88 are formed of a semiconductor layer (source semiconductor layer 92, drain semiconductor layer 93). There is.

In addition, the electronic device which has a wiring film of this invention is not limited to a liquid crystal display device, A board | substrate is also not limited to a glass substrate. The same effect can be exerted when water is present in the surface layer and crystal growth of the film is inhibited. For example, a semiconductor substrate (silicon substrate), a quartz substrate, a resin substrate, a ceramic substrate, or a metal substrate may be used as the substrate.

Example

Hereinafter, although an Example demonstrates this invention, this invention is not limited by these. In addition, about each measurement result of the physical property in a table | surface, blank indicates that it is unmeasured.

[Assessment Methods]

(Measurement of X-ray Diffraction)

X-ray diffraction was measured under the following apparatus and conditions.

Equipment: Ultima III manufactured by Rigaku Corporation

Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]

X-ray source: Cu-Kα ray (Kβ filter not used)

Detector: scintillation counter

Incident side solar slit (vertical) opening angle: 5 °

Receiving Side Solar Slit (Horizontal) Opening Angle: 0.5 °

Tube voltage: 40㎸

Tube current: 40mA

Attenuator (ATT): Open

Dissipation Slit (DS): 1.00 mm

Scattering Slit (SS): Open

Receiver Slit (RS): Open

Scan Mode: 2θ / ω Scan

2θ Scanning Range: Changed by the metal constituting the film. 37.5 to 39.5 ° and 44.0 to 45.5 ° for Al film

Sampling Steps: 0.02 ° / step

Scan Speed: 1 ° / min

In addition, the value in a table | surface and a figure is the value calculated | required from the unprocessed waveform which does not perform various processes (smoothing, BG removal, K (alpha) removal, etc.) with respect to the obtained waveform.

(Distance between peaks of the rocking curve)

In the X-ray diffraction pattern, X-ray diffraction measurement is performed to fix 2θ at the position of the diffraction peak (the angle 2θ = 38.5 ° formed by the incident X-ray direction and the diffraction X-ray direction) resulting from the Al (111) crystal plane. In the diffraction intensity distribution (rocking curve) obtained by changing only the angle? Formed between the incident angle X-rays and the crystal surface and performing X-ray diffraction measurement, instead of the half width, the pseudo-Voight waveform is used to make this waveform a composite waveform of two acids. The distance between the peaks of the two acids at the time of peak fitting as a function was measured.

In the measurement of the rocking curve, the following changes were made from the conditions of the 2θ / ω measurement.

Scan mode: ω scan

ω range: 3 to 33 °

Sampling Step: 0.1 ° / step

Scan Speed: 3 ° / min

In addition, the value in a table | surface and a figure is the value calculated | required from the unprocessed waveform which does not perform various processes (smoothing, BG removal, K (alpha) removal, etc.) with respect to the obtained waveform.

(Dektak film thickness)

Dektak film thickness was measured on condition of the following by Dektak 150 by Al Dr ..

Scantype: StandardScan

Hand radius: 12.5㎛ R

Scan Length: 2000㎛

Time: 13sec

Horizontal resolution: 0.513 μm / data point

Load: 3.00mg

Vertical measuring range: 6.5 μm

Profile: Hills & Valleys

(SEM)

The SU8230 manufactured by Hitachi Hi-Tech Co., Ltd. was observed at 22,000 times and 100,000 times at an acceleration voltage of 2.0 kV or 5.0 kV.

(Section SEM film thickness)

The cross-sectional SEM film thickness calculated the film thickness by contrast with a scale bar based on the image obtained by cross-sectional observation of SEM. In addition, the film thickness calculation method can take other methods, such as cross-sectional observation of a TEM, as long as it can calculate a film thickness with moderate resolution.

(XPS)

XPS was measured on condition of the following by Quantera-SXM by Albac Pa.

X-ray source; AlKα line

Optoelectronic detection angle; 45 ° to the sample surface

Pass energy; 140 eV

Step energy; 0.5 eV / step

Sputter ions; Ar ⁺

Acceleration voltage of sputter ions; 1㎸

Raster size of sputter ions; 2 × 2㎡

The depth direction profile calculates the sputter rate of the thermal oxide film (SiO ₂ film) on a silicon wafer whose film thickness is known in advance, and calculates the conversion depth of the thermal oxide film (SiO ₂ film) on the silicon wafer calculated using this value. It was set as the horizontal axis of the directional profile. Measurement pitch in the depth direction profile was as follows in terms of a 3.0㎚ depth of the thermal oxide film (SiO ₂ film), a silicon wafer. The sputter rate of the thermal oxide film (SiO ₂ film) on the silicon wafer in the example is 2.5 nm / min, and the measurement pitch is 2.5 nm.

Test Example 1 Analysis by X-ray Diffraction

Example 1-1

In Example 1-1, the wiring film was produced as the sputtering apparatus 1 of a 1st example using the vertical inline type sputtering apparatus (made by Shimadzu Corporation) which has a vacuum chamber. The structure of the wiring film 24 according to the embodiment 1-1 is the same as the cross-sectional view shown in FIG. As the substrate 21, a glass substrate having a size of 40 mm Х 40 mm Х thickness 0.5 mm was used.

(Initial Formation)

After holding the substrate 21 in the substrate holder 7, the vacuum chamber 2 is conveyed into the vacuum chamber ^2, and the vacuum chamber ² is evacuated by the vacuum exhaust system 9 so that the pressure is 5.5 to 10 ^-4 kPa. It was set as a vacuum atmosphere. As the sputtering target 11, aluminum (purity: 4N, conveyance direction width: 127 mm, conveyance orthogonal direction width: 559 mm) was used, and the gas of the board | substrate 21 was maintained at 110 degreeC in the gaseous state. Ar gas was introduced as the sputtering gas from the introduction system 8, and when the pressure was stabilized by adjusting the pressure to 4.0 10 10 ⁻¹ kPa, the power was started to supply 2.0 kW of power to the sputtering target 11, thereby supplying the substrate 21. After the sputtering was performed for 2 minutes in a state where the sputtering target 11 was still outside the surface of the sputtering target 11, the target layer was passed through the target front surface at a conveyance speed of 1347 mm / min, and the initial layer 22 was transferred to the substrate 21 by the DC magnetron sputtering method. It formed into a film. By film-forming at this conveyance speed, the film thickness of the initial layer 22 containing aluminum becomes 20 nm.

(The second floor deposition)

When the substrate 21 had passed through the target, the voltage application and the introduction of the sputtering gas were stopped to evacuate. 2.0㎾ of the power pressure is introduced into the Ar gas as a sputtering gas from the gas supply system 8 and then re-evacuating until a 3.4Х10 ^-4 ㎩ and start the power control after the pressure in 4.0Х10 ^-1 ㎩, After supplying to the sputtering target 11 containing aluminum, leaving a board | substrate still outside the surface of the sputtering target 11, presputtering was performed for 2 minutes, and the film thickness of the 2nd layer 23 containing aluminum The target front surface was passed through at a conveyance speed of 47 mm / min so as to be 580 nm, and the second layer 23 was formed on the initial layer 22 by the DC magnetron sputtering method. When the substrate 21 has passed through the front of the target, the introduction of the sputtering gas is stopped and the substrate 21 is taken out of the sputtering apparatus 1, and the wiring formed of the initial layer 22 and the second layer 23 is performed. The membrane 24 was obtained. Table 1 shows the film forming conditions of Example 1-1.

Example 1-2

Under the conditions shown in Table 1, the power supply in the film-forming conditions of the initial layer 22 was set to 1.0 kW, the conveyance speed was set to 1347 mm / min, and the board | substrate 21 was made into the initial layer 22 with a film thickness of 10 nm. After the film was formed on the film, the second layer layer 23 having a film thickness of 590 nm was formed on the initial layer 22 at a conveyance speed of 46 mm / min under the film forming conditions of the second layer 23. A wiring film 24 was obtained in the same manner as in Example 1-1 except for the above.

Example 1-3

On the conditions shown in Table 1, after carrying out film-forming the initial layer 22 with a film thickness of 50 nm on the board | substrate 21 in the film-forming conditions of the initial layer 22 as 540 mm / min, the 2nd layer Example 1-1 except that the second layer 23 having a film thickness of 550 nm was formed on the initial layer 22 at a conveyance speed of 49 mm / min under the film forming conditions of the layer 23. In the same manner, the wiring film 24 was obtained.

Example 1-4

On the conditions shown in Table 1, after carrying out film-forming of the initial layer 22 with a film thickness of 100 nm on the board | substrate 21 on the carrying speed in the film-forming conditions of the initial layer 22 to 270 mm / min, it is 2nd layer. Example 1-1, except that the second layer 23 having a film thickness of 500 nm was formed on the initial layer 22 at a conveyance speed of 54 mm / min under the film forming conditions of the layer 23. In the same manner, the wiring film 24 was obtained.

Example 1-5

Under the conditions shown in Table 1, the power supply in the film-forming conditions of the initial layer 22 was set to 1.0 kW, the conveyance speed was 1346 mm / min, and the initial layer 22 having a film thickness of 10 nm was provided on the substrate 21. After the film was formed on the film, the second layer layer 23 having a film thickness of 90 nm was formed on the initial layer 22 with the conveyance speed under the film forming conditions of the second layer 23 being 302 mm / min. A wiring film 24 was obtained in the same manner as in Example 1-1 except for the above.

Example 1-6

On the conditions shown in Table 1, after carrying out film-forming the initial layer 22 with a film thickness of 20 nm on the board | substrate 21 in the film-forming conditions of the initial layer 22 to 1345 mm / min, it is 2nd layer. Example 1-1, except that the second layer 23 having a film thickness of 80 nm was formed on the initial layer 22 with the conveyance speed in the film forming conditions of the layer 23 of 338 mm / min. In the same manner, the wiring film 24 was obtained.

Example 1-7

On the conditions shown in Table 1, after carrying out film-forming the initial layer 22 with a film thickness of 20 nm on the board | substrate 21 in the film-forming conditions of the initial layer 22 to 1345 mm / min, it is 2nd layer. Example 1-1, except that the second layer 23 having a film thickness of 50 nm was formed on the initial layer 22 at a transport rate of 540 mm / min under the film forming conditions of the layer 23. In the same manner, the wiring film 24 was obtained.

Comparative Example 1-1

On the conditions shown in Table 1, it carried out similarly to Example 1-1 except having formed into a film thickness of 600 nm by one sputter | spatter at 45 mm / min, and obtained the monolayer film.

Comparative Example 1-2

Except having formed into a film thickness of 300 nm each, the conveyance speed at the time of film-forming of the initial layer 22 and the 2nd layer 23 on the conditions shown in Table 1 except having formed into a film thickness of 300 nm, respectively. It carried out similarly to the film | membrane of two layer structure.

Comparative Example 1-3

On the conditions shown in Table 1, it carried out similarly to Example 1-1 except having carried out film formation to 600 nm with one sputter | spatter at 45 mm / min, and obtained the monolayer film.

Comparative Example 1-4

On the conditions shown in Table 1, it carried out similarly to Example 1-1 except having carried out film formation to 100 nm with one sputter | spatter at 271 mm / min, and obtained the monolayer film.

Comparative Example 1-5

On the conditions shown in Table 1, it carried out similarly to Example 1-1 except having carried out film formation to 70 nm with one sputter | spatter at 386 mm / min, and obtained the monolayer film.

Table 1 and Figs. 10 to 13 show the results of evaluation by X-ray diffraction of the test samples obtained in Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-5. In Table 1, "-" represents unevaluated.

As shown in Table 1, Examples 1-1 to 1-4 which are the wiring films of this invention are Al compared with the comparative example 1-1, the comparative example 1-3, and the comparative example 1-4 which are normal single-layer film-forming. (111) peak intensity was high. In Table 1, Comparative Example 1-2, in which the film thickness of the initial layer was more than 200 nm, had a lower Al (111) peak intensity than Examples 1-1 to 1-4.

The Al (111) peak intensity represents the amount (volume) of crystallites oriented in the Al (111) plane, and the larger the numerical value of the Al (111) peak intensity is, the more the crystal grows and the more the crystallites are aligned. Indicates that it is Therefore, it turned out that the wiring film of this invention is excellent in the orientation of a crystal compared with a comparative example.

As shown in Table 1, Examples 1-1 to 1-5, which are the wiring films of the present invention, are Al (111) / Al (200) of 5.0 or more, so that the Al (111) plane has high quality. It can be seen that it consists of a crystal. Further, Examples 1-1 to 1-5, which are the wiring films of the present invention, have a ratio of Al (111) peak intensity and film thickness of two layers of 5.0 [count / nm] or more, so that the orientation of the Al (111) plane is increased. It was found that this is excellent.

10 and 12 are diagrams showing the relationship between the film thickness of the initial layer, the Al (111) peak intensity by X-ray diffraction of the obtained film, and the pressure after vacuum evacuation. As shown in FIG. 10, the pressure after vacuum evacuation (Example 1-1, Comparative Example 1-2) after the film formation of the initial layer and the pressure after vacuum evacuation (Comparative Example 1-1) before the single layer film formation were In spite of the equivalent degree, Example 1-1 had significantly higher Al (111) peak intensity than Comparative Example 1-1 and Comparative Example 1-2. Moreover, as shown in Table 1 and FIG. 12, it can be seen that by setting the film thickness of the initial layer to 3 to 200 nm or less, a wiring film having excellent crystal orientation can be formed without reducing the pressure in the vacuum chamber for a long time. Could.

Fig. 11 is a graph showing the relationship between the pressure after vacuum evacuation and the intensity of the Al (111) peak by X-ray diffraction of the obtained film. As shown in FIG. 11, Example 1-1 had significantly higher Al (111) peak intensity than Comparative Example 1-1 and Comparative Example 1-3.

FIG. 13 is a diagram showing the results of measuring the rocking curve of the Al (111) crystal plane with respect to the films obtained in Comparative Examples 1-1 and Example 1-1. As shown in Table 1 and FIG. 13, Examples 1-1 to 1-4 and Example 1-7 which are the wiring films of this invention compare with the peak of a rocking curve compared with Comparative Examples 1-1 to 1-5. It was found that the distance was small, the alignment film was excellent in crystal orientation and the dispersion of crystal axes was reduced.

From these results, it turned out that according to the method of this invention, the wiring film excellent in the orientation of a crystal can be formed, without reducing the pressure in a vacuum chamber for a long time.

Test Example 2 Observation by SEM

7A and 7B, and FIGS. 8A and 8B are diagrams in which the films obtained in Comparative Examples 1-1 and 1-1 are observed by SEM. 7A and 7B are sectional views (SEM conditions: 2.0 kPa, 22,000 times), and FIG. 7B is an enlarged view of Example 1-1 in FIG. SEM conditions: 2.0 kPa, 100,000 times). 8 (a) and 8 (b) are diagrams of SEM observation of the surfaces of the films obtained in Comparative Examples 1-1 and 1-1, respectively (observation conditions: 5.0 kPa, 100,000 times). . As shown in Figs. 7A and 7B, in Comparative Example 1-1, the film was continuously grown, while in Example 1-1, the boundary between the initial layer and the second layer was clearly present and thus discontinuous. have. Thus, by observing a film cross section by SEM, it can prove that it is a wiring film of the 1st aspect and 2nd aspect of this invention. Although SEM observation was illustrated as proof of the wiring film of a 1st aspect and a 2nd aspect, a proof is not limited to this.

As shown in (a) and (b) of FIG. 7 and (a) and (b) of FIG. 8, the ratio of crystals having a large particle size as a whole is greater in Example 1-1 than in Comparative Example 1-1. There was a tendency to increase, and also the variation of the particle diameter was small. Moreover, the surface roughness also fell.

Test Example 3 Analysis by XPS

9 (a) and 9 (b) show the results of depth direction analysis of the films obtained in Comparative Examples 1-5 and Example 1-7 from the Al film surface toward the glass side by XPS. Table 2 also shows the compositions of O and Al with respect to the depth from the surface read from this data.

In Comparative Example 1-5, a depth of about 0 to 10 nm is a region in which an air oxide layer on the surface exists, and a depth of about 10 to 60 nm is a region in which a single layer Al film exists, and a single layer Al over a depth of about 60 to 80 nm. It is the area where film and glass exist. In the region of about 60 to 80 nm in depth, the amount of oxygen atoms is increased. At a depth of about 50 nm, the amount of oxygen atoms is 0 atomic%. In Example 1-7, the depth of about 0-10 nm is the area | region where the surface air oxide layer exists similarly, the depth of about 10-40 nm is the area | region where the 2nd Al film exists, and the depth of about 40-60 nm is 2 It is a region where the Al film and the initial layer of the layer exist, and a depth of about 60 to 80 nm is a region where the initial layer and glass exist. In Example 1-7, it turns out that the amount of oxygen atoms of about 40-60 nm in depth is increasing, and the oxygen atom amount shows the maximum in the vicinity of about 50 nm, and is 5 atomic%. At this time, the interlayer oxygen atom content ratio is 12.5 and the initial layer oxygen atom content ratio is 0.053.

As described above, it was found that the amount of oxygen atoms in the initial layer of Example 1-7 was larger than that of Comparative Example 1-5. This result is that Example 1-7 reacts with the moisture adhering to the substrate, and / or the initial layer is formed while the water is sputtered out by the sputter, so that the film is formed after the glass surface moisture is splashed out. It is estimated that there is a lot of water retention.

Test Example 4 Analysis by X-ray Diffraction

Example 2-1

In Example 2-1, as a sputtering apparatus 1 of a 1st example, the wiring film was produced using the vertical inline type sputtering apparatus (made by Shimadzu Corporation) which has a vacuum chamber. In the same manner as in Example 1-1, except that molybdenum (purity: 4N, conveyance direction width: 127 mm, conveyance orthogonal direction width: 559 mm) was used as the sputtering target 11 under the conditions shown in Table 2. And the wiring film 24 was obtained.

Comparative Example 2-1

On the conditions shown in Table 2, it carried out similarly to Example 2-1 except having formed into a film thickness of 300 nm with one sputter | spatter at the conveyance speed of 101 mm / min, and obtained the monolayer film.

Table 2 shows the results of evaluation of the obtained test samples by X-ray diffraction. The 2θ scan range of the Mo film was measured in a range covering the diffraction line position from each (hkl) plane of the crystal as shown below.

Mo (110): 39.0 to 41.0 °, Mo (211): 73.0 to 75.0 °

As shown in Table 3, although the pressure after vacuum evacuation (Example 2-1) after film-forming of an initial layer, and the pressure after vacuum evacuation (Comparative Example 2-1) before single-layer film deposition are about the same, In Example 2-1, Mo (110) peak intensity and Mo (110) / Mo (211) were significantly higher than those of Comparative Example 2-1. Therefore, according to the method of this invention, it turned out that the wiring film excellent in the orientation of a crystal can be formed, without reducing the pressure in a vacuum chamber for a long time.

Test Example 5 Analysis by X-ray Diffraction

Example 3-1

In Example 3-1, the wiring film was produced as the sputtering apparatus 1 of a 1st example using the vertical inline type sputtering apparatus (made by Shimadzu Corporation) which has a vacuum chamber. Under the conditions shown in Table 3, the sputtering target 11 was used in the same manner as in Example 1-1 except that titanium (purity: 4N, conveyance direction width: 127 mm, conveyance orthogonal direction width: 559 mm) was used. And the wiring film 24 was obtained.

Comparative Example 3-1

On the conditions shown in Table 3, it carried out similarly to Example 3-1 except having formed into a film thickness of 300 nm with one sputter | spatter at a conveyance speed of 73 mm / min, and obtained the monolayer film.

Table 4 shows the results of evaluation of the obtained test samples by X-ray diffraction. The 2θ scan range of the Ti film was measured in the range covering the diffraction line position from each (hkl) plane of the crystal as shown below.

Ti (002): 37.0 to 39.0 °, Ti (004): 81.5 to 83.5 °

As shown in Table 4, although the pressure after vacuum evacuation (Example 3-1) after the film-forming of an initial layer, and the pressure after vacuum evacuation (Comparative Example 3-1) before a single-layer film deposition are about the same, In Example 3-1, the Ti (002) peak intensity and Ti (002) / Ti (004) were significantly higher than those of Comparative Example 3-1. Therefore, according to the method of this invention, it turned out that the wiring film excellent in the orientation of a crystal can be formed, without reducing the pressure in a vacuum chamber for a long time.

Test Example 6 Analysis by X-ray Diffraction

Example 4-1

In Example 4-1, copper (purity: 4N, conveyance direction width: 70 mm, conveyance) is used as the sputtering target 11 using the inline sputtering apparatus (manufactured by Nichima Seiki) under the conditions shown in Table 5. The wiring film 24 was obtained like Example 1-1 except having used the thing containing orthogonal direction width: 200 mm.

Comparative Example 4-1

On the conditions shown in Table 5, it carried out similarly to Example 4-1 except having formed into a film thickness of 300 nm with one sputter | spatter at the conveyance speed of 66 mm / min, and obtained the monolayer film.

Table 5 shows the results of evaluation of the obtained test samples by X-ray diffraction.

As shown in Table 5, Example 4-1, which is the wiring film of the present invention, has a higher value of Cu (111) / Cu (200) than Comparative Example 4-1, indicating that crystal orientation is excellent. there was.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on Japanese Patent Application No. 2018-076267 for which it applied on April 11, 2018, and Japanese Patent Application No. 2019-073658 for which it applied on April 8, 2019, The content is referred here as a reference. It is used.

Claims (40)

It is a wiring film of a multilayer structure provided on a board | substrate,
An initial layer comprising a metal or an alloy composed of a metal element having a film thickness of 3 to 200 nm, or a compound thereof formed on the substrate;
A wiring film comprising a second or later layer comprising a metal or an alloy composed of a metal element formed on the initial layer or a compound thereof, and having an interface between the initial layer and the second layer. The method of claim 1,
The main film | membrane of the said initial layer and the layer after the 2nd layer consists of a metal or alloy of the same kind, or its compound, The wiring film characterized by the above-mentioned. The method according to claim 1 or 2,
The wiring film, wherein the initial layer is an oxygen atom-containing layer. The method of claim 3,
The interlayer oxygen atom content rate is two or more, The wiring film characterized by the above-mentioned. The method of claim 4, wherein
The initial layer oxygen atom content rate is 0.02-1.5, The wiring film characterized by the above-mentioned. The method according to any one of claims 1 to 5,
The metal element is Al, Cu, Ti, Mo, C, Si, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Zr, Nb, Ru, Rh, Pd, Ag, Cd And In, Sn, Sb, Te, Ta, W, Ir, Pt, Au, Pb, Ru and Bi, at least one selected from the group consisting of a wiring film. It is a wiring film of the multilayered structure containing a metal element provided on the board | substrate by sputtering in a vacuum atmosphere,
An initial layer having a film thickness of 3 to 200 nm deposited on the substrate;
And a second layer or later layer formed on the initial layer after evacuating after the deposition of the initial layer. The method of claim 7, wherein
The wiring film whose pressure after vacuum evacuation after the film formation of the said initial layer is 1.0x10 <^-3> Pa or less. The method according to claim 7 or 8,
Al, Cu, Ti, Mo, C, Si, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Zr, Nb, Ru, Rh, Pd, Ag, Cd, In, Sn, A wiring film composed of a metal or an alloy of at least one metal element selected from the group consisting of Sb, Te, Ta, W, Ir, Pt, Au, Pb, Ru, and Bi, or a compound thereof. The method according to any one of claims 1 to 9,
The wiring film whose ratio of the largest 1st diffraction peak and the next largest 2nd diffraction peak and the 1st diffraction peak / 2nd diffraction peak among the diffraction peaks resulting from the specific crystal surface obtained by X-ray diffraction is 5.0 or more. The method according to any one of claims 1 to 9,
The ratio of the largest first diffraction peak and the next largest second diffraction peak, the first diffraction peak / second diffraction, among the diffraction peaks due to a specific crystal plane obtained by X-ray diffraction with a film thickness of 200 nm or less The wiring film whose peak is 2.3 or more. The method according to any one of claims 1 to 11,
Among the diffraction peaks resulting from the specific crystal plane obtained by X-ray diffraction, the ratio of the largest first diffraction peak to the next largest second diffraction peak, the first diffraction peak / second diffraction peak, is obtained by sputtering the substrate. A wiring film which is at least 5% larger than a wiring film made of the same film thickness formed on the film and a single layer having the same composition as the initial layer. The method according to any one of claims 1 to 12,
A wiring film containing Al or Cu as a main component. The method of claim 13,
Al (111) / Al (200) is a wiring film mainly composed of Al, and the ratio of diffraction peaks attributable to the Al (111) crystal plane obtained by X-ray diffraction and diffraction peaks attributable to the Al (200) crystal plane A wiring film which is 5.0 or more. The method of claim 13,
A wiring film containing Al as a main component, the film thickness being 200 nm or less, and the ratio of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction and the diffraction peak resulting from the Al (200) crystal plane, Al (111). ) / Al (200) is a wiring film of 2.3 or more. The method of claim 13,
A wiring film having Al as a main component and having a half width (2θ) of a diffraction peak resulting from an Al (111) crystal plane obtained by X-ray diffraction measured according to the following conditions, which is 0.38 ° or less.
Equipment: Ultima III manufactured by Rigaku Corporation
Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]
X-ray source: Cu-Kα ray (Kβ filter not used)
Tube voltage: 40㎸
Tube current: 40mA
Sampling Steps: 0.02 ° / step
Scan Speed: 1 ° / min The method of claim 13,
A wiring film having Al as a main component, wherein the distance between peaks when the rocking curve is measured at the position of the diffraction peak due to the Al (111) crystal plane is 15 ° or less. The method of claim 13,
A wiring film having a two-layer structure containing Al as a main component, and the ratio of the intensity of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction measured under the following conditions to the film thickness of the two layers is 5.0 [count / Nm] or more.
Equipment: Ultima III manufactured by Rigaku Corporation
Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]
X-ray source: Cu-Kα ray (Kβ filter not used)
Tube voltage: 40㎸
Tube current: 40mA
Sampling Steps: 0.02 ° / step
Scan Speed: 1 ° / min The method of claim 13,
The same film thickness and the initial layer in which a half width (2θ) of a diffraction peak resulting from an Al (111) crystal plane obtained by X-ray diffraction is a wiring film mainly composed of Al, formed on the substrate by sputtering. A wiring film, which is at least 5% smaller than a wiring film composed of a single layer having the same composition as the composition. The method of claim 13,
Cu (111) / Cu (200) is a wiring film mainly composed of Cu, and the ratio of diffraction peaks due to the Cu (111) crystal plane obtained by X-ray diffraction and diffraction peaks due to the Cu (200) crystal plane A wiring film which is 5.0 or more. The method of claim 13,
The wiring film which has Cu as a main component, and whose half value width (2theta) of the diffraction peak resulting from the Cu (111) crystal surface obtained by X-ray diffraction measured by the following conditions is 0.38 degrees or less.
Equipment: Ultima III manufactured by Rigaku Corporation
Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]
X-ray source: Cu-Kα ray (Kβ filter not used)
Tube voltage: 40㎸
Tube current: 40mA
Sampling Steps: 0.02 ° / step
Scan Speed: 1 ° / min The method of claim 13,
The same film thickness and the initial layer in which the half width (2θ) of the diffraction peak resulting from the Cu (111) crystal plane obtained by X-ray diffraction is a wiring film containing Cu as a main component, and is formed on the substrate by sputtering. A wiring film, which is at least 5% smaller than a wiring film composed of a single layer having the same composition as the composition. The method according to any one of claims 1 to 22,
A wiring film, wherein the substrate is a glass substrate, a silicon substrate, a quartz substrate, a resin substrate, a ceramic substrate, or a metal substrate. It is a method of forming the wiring film of the multilayered structure containing a metal element by sputtering in a vacuum atmosphere,
Vacuum-exhaust after depositing an initial layer having a film thickness of 3 to 200 nm on the substrate, and
And depositing a layer after the second layer on the initial layer. The method of claim 24,
The pressure after vacuum evacuation after film formation of the said initial layer is 1.0 * 10 <^-3> Pa or less. The method of claim 24 or 25,
The wiring film is Al, Cu, Ti, Mo, C, Si, Cr, Mn, Fe, Co, Ni, Zn, Ga, Ge, As, Se, Zr, Nb, Ru, Rh, Pd, Ag, Cd, A method comprising a metal or an alloy of at least one metal element selected from the group consisting of In, Sn, Sb, Te, Ta, W, Ir, Pt, Au, Pb, Ru, and Bi, or a compound thereof. The method according to any one of claims 24 to 26,
The wiring film has a ratio between the largest first diffraction peak and the next largest second diffraction peak and the first diffraction peak / second diffraction peak among the diffraction peaks due to the specific crystal plane obtained by X-ray diffraction, being 5.0 or more. , Way. The method according to any one of claims 24 to 26,
The wiring film has a film thickness of 200 nm or less, and among the diffraction peaks resulting from the specific crystal plane obtained by X-ray diffraction, the ratio of the largest first diffraction peak to the next largest second diffraction peak, the first diffraction peak / Second diffraction peak is at least 2.3. The method according to any one of claims 24 to 28,
Among the diffraction peaks resulting from the specific crystal plane obtained by X-ray diffraction, the wiring film is sputtered by a ratio between the largest first diffraction peak and the next largest second diffraction peak and the first diffraction peak / second diffraction peak. And at least 5% larger than a wiring film composed of the same film thickness deposited on the substrate and a single layer having the same composition as the initial layer. The method according to any one of claims 24 to 29, wherein
The said wiring film has Al or Cu as a main component. The method of claim 30,
The wiring film is a wiring film mainly composed of Al, and is a ratio of diffraction peaks due to the Al (111) crystal plane obtained by X-ray diffraction and diffraction peaks due to the Al (200) crystal plane, and Al (111) / Al. The method, wherein 200 is 5.0 or more. The method of claim 30,
The wiring film is a wiring film mainly composed of Al, has a film thickness of 200 nm or less, and a ratio of diffraction peaks due to the Al (111) crystal plane obtained by X-ray diffraction and diffraction peaks due to the Al (200) crystal plane. , Al (111) / Al (200) is 2.3 or more. The method of claim 30,
The said wiring film is a wiring film which has Al as a main component, and the half value width (2 (theta)) of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction measured by the following conditions is 0.38 degrees or less.
Equipment: Ultima III manufactured by Rigaku Corporation
Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]
X-ray source: Cu-Kα ray (Kβ filter not used)
Tube voltage: 40㎸
Tube current: 40mA
Sampling Steps: 0.02 ° / step
Scan Speed: 1 ° / min The method of claim 30,
The said wiring film is a wiring film which has Al as a main component, and the distance between peaks when the rocking curve is measured at the position of the diffraction peak resulting from Al (111) crystal plane is 15 degrees or less. The method of claim 30,
The wiring film is a wiring film having a two-layer structure containing Al as a main component, and the ratio of the intensity of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction measured by the following conditions to the film thickness of the two layers. The method of 5.0 [count / nm] or more.
Equipment: Ultima III manufactured by Rigaku Corporation
Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]
X-ray source: Cu-Kα ray (Kβ filter not used)
Tube voltage: 40㎸
Tube current: 40mA
Sampling Steps: 0.02 ° / step
Scan Speed: 1 ° / min The method of claim 30,
The wiring film is a wiring film mainly composed of Al, and has the same film thickness formed on the substrate by sputtering at a half width (2θ) of the diffraction peak resulting from the Al (111) crystal plane obtained by X-ray diffraction. And at least 5% smaller than a wiring film composed of a single layer having the same composition as the initial layer. The method of claim 30,
The wiring film is a wiring film containing Cu as a main component, and the ratio of the diffraction peak due to the Cu (111) crystal plane obtained by X-ray diffraction and the diffraction peak due to the Cu (200) crystal plane, Cu (111) / Cu The method, wherein 200 is 5.0 or more. The method of claim 30,
The said wiring film is a wiring film which has Cu as a main component, and the half value width (2 (theta)) of the diffraction peak resulting from the Cu (111) crystal plane obtained by X-ray diffraction measured by the following conditions is 0.38 degrees or less.
Equipment: Ultima III manufactured by Rigaku Corporation
Optical System: Parallel Beam Optical System (PB) [Thin Film (General)]
X-ray source: Cu-Kα ray (Kβ filter not used)
Tube voltage: 40㎸
Tube current: 40mA
Sampling Steps: 0.02 ° / step
Scan Speed: 1 ° / min The method of claim 30,
The wiring film is a wiring film containing Cu as a main component, and the same film thickness in which the half width (2θ) of the diffraction peak resulting from the Cu (111) crystal plane obtained by X-ray diffraction is formed on the substrate by sputtering. And at least 5% smaller than a wiring film composed of a single layer having the same composition as the initial layer. The method according to any one of claims 24 to 39, wherein
And said substrate is a glass substrate, a silicon substrate, a quartz substrate, a resin substrate, a ceramic substrate, or a metal substrate.

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