JP2003170524A - LAMINATE HAVING Ag-BASED FILM AND METHOD FOR FORMING Ag-BASED FILM - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming an Ag-based film having the good adhesion with a substrate and to provide a laminate having the Ag-based film. <P>SOLUTION: An oxide film 2 of an Ag-based material is formed on the substrate 1 and the Ag-based film 3 comprising the Ag-based material is formed on the oxide film 2 to form the laminate 10 wherein the oxide film 2 of the Ag-based material is interposed between the substrate 1 and the Ag-based film 3. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a method for forming an Ag-based film for forming a g-alloy film and a laminate having this Ag-based film, and more specifically to a technique for increasing the adhesion of the Ag film or the Ag-alloy film to a substrate.

[0002]

2. Description of the Related Art Ag films and Ag alloy films are used for liquid crystals and organic E
It is used for thin film wirings, electrodes, reflective films, etc. for display devices using L (Electro Luminescence) elements and the like. A
If the film thickness of the g film or the Ag alloy film is thin, it becomes a conductive film having good light transmissivity, and if it is thick, it becomes a conductive film having good light reflectivity. For example, in an organic EL element, a transparent electrode is formed on a glass substrate, and as the transparent electrode, an Ag film or A
A g-alloy film is used.

[0003]

However, Ag films and Ag films
The alloy film has poor adhesion to a substrate such as a glass substrate as an underlayer. For example, if it goes through a photoresist process when patterning an Ag film or an Ag alloy film, peeling from the substrate easily occurs and stability is improved. Was missing.

The present invention has been made in view of the above problems, and an object of the present invention is to obtain a good adhesion to a substrate A.
A method for forming a g-based film and a laminate having such an Ag-based film.

[0005]

A laminate having an Ag-based film according to the present invention is constructed by interposing an oxide film of the Ag-based material between a substrate and an Ag-based film made of an Ag-based material. It

In the method of forming an Ag-based film of the present invention, an oxide film of an Ag-based material is formed on a substrate, and then an Ag-based film made of the Ag-based material is formed on the oxide film. To do.

That is, in the present invention, before forming the Ag film or the Ag alloy film on the substrate, the respective oxide films (A
After forming the gO _x film and the Ag alloy O _x film), the Ag film or the Ag alloy film is laminated to provide the adhesiveness with the substrate. Preferably, AgO _x film and Ag alloy O
_{If the X} film and each film thickness is 20 Å or more, more excellent adhesion can be obtained.

In the present invention, the Ag-based material means Ag alone or Ag containing, for example, Cu, Ti, Su, Au, Pt,
It represents an Ag alloy formed by adding one or more of Ni and the like. The base has a single layer structure such as a glass substrate or a plastic substrate, or a multilayer structure in which a TiO _x film or a SiO ₂ film is formed on the glass substrate or the plastic substrate.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a film forming apparatus used in this embodiment will be described with reference to FIGS. In the present embodiment, film formation is carried out using a pass film formation type interback type sputtering device 30. FIG. 5 shows the sputtering apparatus 3
0 is a schematic side view, and FIG. 6 is a schematic plan view.

The sputtering apparatus 30 mainly comprises a sputtering chamber 31 and a loading / unloading chamber 32. Both chambers 31 and 32 are partitioned by a sluice valve 36. The sluice valve 36 can hermetically shut off the both chambers 31 and 32. The loading / unloading chamber 32 is evacuated through a valve 38 to a vacuum exhaust system (roughing system).
It is connected to the. The sputtering chamber is connected to a vacuum pump (eg, cryopump) 40 via a valve 39.

The substrate 1 is held by a carrier 35 with the surface on which the film is formed being exposed downward, and is carried in and out by a carrier chamber 32 and a sputtering chamber 31.
And the inside of the sputtering chamber 31 is moved to the left and right in the figure. The carrier 35 is supported on both side ends by rollers (not shown) arranged along the moving direction, and moves on the rollers.

A target 33 is provided on the entrance / exit side (right side in the drawing) of the sputtering chamber 31, and power is applied from a power source 41 to the target 33 during film formation. In the vicinity of the target 33, a gas introduction pipe 37 communicating with the inside of the sputtering chamber 31 is provided. Sputtering room 31
A heater 34a is arranged on the left side of the inside to form a heating portion 34.

(First Embodiment) The substrate 1 has a vertical and horizontal dimensions of 210 mm × 210 mm and a thickness of 0.7 mm.
A Corning Code 7059, 1737 glass substrate was used. The target 33 is made of an Ag material having a purity of 99.99% or more.

First, the glass substrate 1 is held by the carrier 35 and loaded into the loading / unloading chamber 32. Then, the inside of the carry-in / out chamber 32 is roughly exhausted. The interior of the sputtering chamber 31 is evacuated by the cryopump 40. When both chambers 31 and 32 have a predetermined reduced pressure atmosphere, the sluice valve 36 is opened, and the glass substrate 1 is carried into the sputtering chamber 31 by the movement of the carrier 35.

The glass substrate 1 is moved to and heated by a heating section 34 provided with a heater 34a. At this time, Ar gas and O ₂ gas are introduced from the gas introduction pipe 37 (vacuum evacuation is continued), and the inside of the sputtering chamber 31 is filled with Ar gas.
Mixed gas atmosphere of gas and O ₂ gas (pressure 0.3 Pa)
It is said that

In the atmosphere described above, power is applied to the Ag target 33 from the power source 41, and the glass substrate 1 heated by the heating unit 34 is placed in the sputtering chamber 31 (heating unit 3).
Move to the left or right with the part other than 4. As a result, Ag
Ag atoms sputtered from the target 33 adhere to the glass substrate 1 while reacting with the O ₂ gas to form an AgO _x film on the glass substrate 1. The reason why the sputtering is performed while moving the glass substrate 1 is to make the film thickness uniform within the substrate surface.

When the application of electric power to the Ag target 33 is stopped and the formation of the AgO _x film is completed, the glass substrate 1 is moved to the heating section 34 again, the introduction of O ₂ gas is stopped, and the discharge is performed. The Ar gas for use is introduced at 120 sccm, and the inside of the sputtering chamber 31 is set to an atmosphere of Ar gas only (pressure 0.3 Pa).

Then, in this Ar gas atmosphere, power is applied to the Ag target 33 from the power source 41, and the glass substrate 1 heated by the heating section 34 is moved to the sputtering chamber 3
It is moved left and right within 1 (a part other than the heating part 34). Thereby, the Ag sputtered from the Ag target 33
Atoms adhere to the glass substrate 1 and an Ag film is formed on the glass substrate 1. Also during this film formation, the sputtering is performed while moving the glass substrate 1 in order to make the film thickness uniform within the substrate surface. In addition, during the above series of film forming steps,
The gate valve 36 is closed, and the sputter chamber 31 and the carry-in / out chamber 32 are
And airtightly cut off.

When the above-described series of film formation is completed, Ag
O _X film and the glass substrate 1, an Ag film is laminated via a gate valve 36 which is opened and transport room under reduced pressure 3
It is transported to the 2 and taken out. In this way
The laminated body 10 shown in FIG. 1 is obtained. That is, the laminated body 1
In No. 0, the AgO _x film 2 is formed on the glass substrate 1, and the Ag film 3 is formed on the AgO _x film 2. Thus, by stacking the Ag film 3 on glass substrate 1 through the AgO _X film 2, between the Ag film 3 and AgO _X film 2, and AgO _X film 2 and to increase the adhesion between the glass substrate 1 It is possible to prevent film peeling.

The results of the peeling test conducted to evaluate the adhesion will be described below. This test is to confirm the peeling of the Ag film 3 by sticking an adhesive tape on the surface (Ag film 3) of the laminate 10 obtained above and then peeling off the tape. Specifically, a Nichiban cellophane tape cut into a length of 3 cm and a 3M Scotch tape with a stronger adhesive strength (again, length 3c
m). As shown in FIG. 7, the test was performed at nine positions (indicated by numbers 1 to 9) on the laminate 10.
The thickness of the AgO _x film 2 is about 20 Å to 100 Å, and the partial pressure of O ₂ gas (partial pressure for a total pressure of 0.3 Pa) when forming the AgO _x film 2 is 0.01.
Pa to 0.3 Pa.

Further, a peeling test similar to that described above was carried out, and a laminate having a conventional structure in which an Ag film was directly formed on a glass substrate (produced under the same sputtering apparatus and conditions as above)
Also went. The result of this comparison is shown in FIG. Figure 8
Medium, Pos.1 to Pos.9 correspond to positions 1 to 9 in FIG. Further, in FIG. 8, the term “temperature” indicates the temperature of the glass substrate during film formation (for example, measured by attaching a thermocouple to the glass substrate). Room temperature is when the glass substrate is not heated.

In FIG. 8, .largecircle. Indicates that no peeling occurred, x indicates peeling, and .DELTA. Indicates slight peeling as an evaluation between .largecircle. And x. As is clear from this result, it can be seen that the structure of (Ag / AgO _x / glass substrate) is superior in adhesiveness to the conventional structure (Ag / glass substrate). In particular, when a glass substrate was heated at 150 ° C. to form a film, peeling was not observed at all positions.

FIG. 9 shows Ar during the formation of the AgO _x film.
The adhesion evaluation when the mixing ratio of gas and O ₂ gas is changed is shown. The AgO _x film was formed with a film thickness of 100 Å. As can be seen from this result, the partial pressure of O ₂ gas is 0 P.
When a, i.e. other than when not formed AgO _X film (conventional configuration) is a better result. That is, even a small amount of O ₂ gas is introduced to oxidize Ag.
By interposing the film (AgO _x film) between the glass substrate and the Ag film, the adhesion can be improved as compared with the conventional case. Although not shown in FIG. 9, good adhesion was obtained even when the partial pressure of O ₂ gas was 0.01 Pa.

FIG. 10 shows the relationship between the film thickness of the AgO _x film and the peeling rate. The atmosphere during deposition of the AgO _x film is 0.2 Pa.
Of Ar gas and O ₂ gas of 0.1 Pa (total pressure P _tot is 0.3 Pa). ● is the substrate temperature 1
As a result of film formation at 50 ° C., × indicates the result of film formation at room temperature. As can be seen from these results, regardless of the substrate temperature, when the thickness of the AgO _x film was 20 Å or more, the peeling rate was 0%, and peeling was not observed. Therefore,
If the thickness of the AgO _x film is 20 Å or more, excellent adhesion can be obtained. The film thickness can be easily controlled by adjusting the power applied to the Ag target 33 and the gas flow rates of Ar gas and O ₂ gas introduced into the sputtering chamber 31. In addition, AgO
_The Ag film formed on the _X film has a thickness of 1000 to 50.
It is 00Å.

(Second Embodiment) In the present embodiment,
An Ag alloy film (specifically, an alloy film of Ag and Cu) was formed as an Ag-based film. Also in this embodiment, FIGS.
Interpenetrating type sputtering apparatus 30 shown in FIG.
Was used to form a film.

As in the first embodiment, the substrate 1 has vertical and horizontal dimensions of 210 mm × 210 mm and a thickness of 0.
A 7 mm Corning Code 7059, 1737 glass substrate was used. The target 33 is made of an Ag material having a purity of 99.99% or more. Further, in the present embodiment, a Cu chip (3 to 5 mm square) is placed on the Ag target 33.
As a result, an Ag alloy film (Ag: Cu = 97 at%: 3 at%) containing 3 at% (atomic weight%) of Cu is formed.

First, as in the first embodiment, the glass substrate 1 is held by the carrier 35 and loaded into the loading / unloading chamber 32. Then, the inside of the carry-in / out chamber 32 is roughly exhausted.
The interior of the sputtering chamber 31 is evacuated by the cryopump 40. When both chambers 31 and 32 have a predetermined reduced pressure atmosphere,
The sluice valve 36 is opened, and the glass substrate 1 is carried into the sputtering chamber 31 by the movement of the carrier 35.

The glass substrate 1 is moved to and heated by the heating section 34 provided with the heater 34a. At this time, Ar gas and O ₂ gas are introduced from the gas introduction pipe 37 (vacuum evacuation is continued), and the inside of the sputtering chamber 31 is filled with Ar gas.
Mixed gas atmosphere of gas and O ₂ gas (pressure 0.3 Pa)
It is said that

In the above atmosphere, power is applied from the power source 41 to the Ag target 33 on which the Cu chip is mounted, and the glass substrate 1 heated by the heating section 34 is placed in the sputtering chamber 31 (other than the heating section 34). Part) to move left and right. As a result, the Ag target 33 and Cu on the Ag target 33 are formed.
Ag atoms and Cu atoms sputtered from the chips adhere to the glass substrate 1 while reacting with O ₂ gas to form an (Ag—Cu alloy) O _x film on the glass substrate 1. Performing sputtering while moving the glass substrate 1 is
This is to make the film thickness uniform within the substrate surface.

When the application of electric power to the Ag target 33 is stopped and the formation of the (Ag-Cu alloy) O _x film is completed, the glass substrate 1 is moved to the heating section 34 again, and further O ₂ gas is introduced. Stop, and only discharge Ar gas for 120s
It is introduced at ccm, and the inside of the sputtering chamber 31 is set to an atmosphere of Ar gas only (pressure 0.3 Pa).

Then, in this Ar gas atmosphere, electric power is applied to the Ag target 33 from the power source 41, and the glass substrate 1 heated by the heating section 34 is moved to the sputtering chamber 3
It is moved left and right within 1 (a part other than the heating part 34). As a result, the alloy film of Ag atoms and Cu atoms sputtered from the Ag target 33 and the Cu chip becomes the glass substrate 1.
Is formed. Also during this film formation, the sputtering is performed while moving the glass substrate 1 in order to make the film thickness uniform within the substrate surface. During the above-described series of film forming steps, the sluice valve 36 is closed, and the sputtering chamber 31 and the loading / unloading chamber 32 are hermetically shut off from each other.

When the series of film formation described above is completed, (A
The glass substrate 1 on which the g-Cu alloy) O _x film and the Ag-Cu alloy film are laminated is conveyed to the loading / unloading chamber 32 under reduced pressure via the sluice valve 36 in the open state and taken out to the outside. Be done. In this way, the laminated body 20 shown in FIG. 2 is obtained. That is, in the laminated body 20, the (Ag—Cu alloy) O _X film 12 is formed on the glass substrate 1, and the (Ag—Cu alloy) O _X film 12 is formed.
-Cu alloy) O _X film formed is formed Ag-Cu alloy film 13 on 12. Thus, (Ag-Cu alloy)
By stacking the Ag—Cu alloy film 13 on the glass substrate 1 through the O _x film 12, the Ag—Cu alloy film 13 and (Ag−
Between Cu alloy) O _X film 12, and (Ag-Cu alloy) O _X
The adhesion between the film 12 and the glass substrate 1 can be increased,
Film peeling can be prevented.

Also in this embodiment, the same adhesion evaluation as in the first embodiment was performed. FIG. 11 shows (Ag-C
u alloy) Evaluation of adhesion when changing the mixing ratio of Ar gas and O ₂ gas during formation of O _x film. In addition,
(Ag-Cu alloy) O _X film was formed to a thickness of 100 Å. As can be seen from this result, the partial pressure of O ₂ gas is 0 P.
In the case of “a”, that is, except when the (Ag—Cu alloy) O _x film was not formed (conventional structure), the result is good. That is, even if only a small amount of O ₂ gas is introduced and the oxidized Ag—Cu alloy film is interposed between the glass substrate and the Ag—Cu alloy film, the adhesion can be improved as compared with the conventional case. . Although not shown in FIG. 11, good adhesion was obtained even when the partial pressure of O ₂ gas was 0.01 Pa.

FIG. 12 shows the relationship between the film thickness of the (Ag—Cu alloy) O _x film and the peeling rate. (Ag—Cu alloy) O _X film is formed in an atmosphere of Ar gas of 0.2 Pa and 0.1 P
Gas mixture of a with O ₂ gas (total pressure P _tot is 0.3
Pa). ● is the result of film formation at a substrate temperature of 150 ℃,
X indicates the result of film formation at room temperature. As can be seen from these results, regardless of the substrate temperature, (Ag-Cu alloy) O _x
When the film thickness was 20 Å or more, the peeling rate was 0%, and peeling was not observed. Therefore, (Ag-Cu
_{If the} film thickness of the alloy) O _x film is 20 Å or more, excellent adhesion can be obtained. The film thickness can be easily controlled by adjusting the power applied to the Ag target 33 on which the Cu chip is mounted, the gas flow rates of Ar gas and O ₂ gas introduced into the sputtering chamber 31, and the like. Incidentally, the thickness of the (Ag-Cu alloy) O _X film Ag-Cu alloy film formed on the, 1000-5000
It is Å.

Although the respective embodiments of the present invention have been described above, it goes without saying that the present invention is not limited to these embodiments.
Various modifications are possible based on the technical idea of the present invention.

The various conditions at the time of film formation by sputtering shown in each of the above embodiments are not limited to those shown above. Further, the formation of the Ag-based oxide film is not limited to reactive sputtering using O ₂ gas, but may be performed by sputtering a target made of an Ag-based oxide in an atmosphere of only an inert gas. Good. However, in this case, there are problems such as the workability of the target made of an Ag-based oxide and the composition of the obtained Ag-based oxide film deviating from the composition of the target. On the other hand, in forming the Ag-based oxide film by reactive sputtering, O ₂
By changing the mixing ratio of the gas and the inert gas and performing the sputtering, the Ag-based oxide film can be easily controlled to have a desired composition. By simply controlling the gas to be introduced, it is efficient to continuously form the Ag-based oxide film and the Ag-based film in the same sputtering chamber. In the process of forming the Ag-based oxide film and the Ag-based film, the sputtering chamber is not broken in vacuum, that is, not exposed to the atmosphere, so that a good quality film can be obtained. There are advantages such as. The discharge gas during sputtering is not limited to Ar gas, and other inert gas can be used. Further, the laminated body having the structure shown in FIGS. 1 and 2 may be produced by not only sputtering but also vapor deposition, for example.

The substrate is not limited to the glass substrate, but may be any of those shown in FIG.
Even when the plastic substrate 21 is used as shown in FIG. 5, an Ag-based oxide film (AgO _x film /
Good adhesion with the Ag alloy O _x film) 22 and the Ag-based film (Ag film / Ag alloy film) 23 can be obtained. Further, as the base, as shown in FIG. 4, Ti on the glass substrate 1 is used.
It may have a multi-layer structure in which an O _x film or a SiO ₂ film is formed. Of course, it may have a multi-layer structure in which a TiO _x film or a SiO ₂ film is formed on the plastic substrate 21. Further, as an Ag-based alloy, Ag-
Not only Cu alloys but also Ag, such as Cu, Ti, Su,
It may be an Ag alloy formed by adding one or more of Au, Pt, Ni and the like.

[0038]

As described above, according to the present invention, by interposing an oxide film of Ag or an oxide film of Ag alloy between the substrate and the Ag film or the Ag alloy film, Ag on the substrate is improved. The adhesion of the film or the Ag alloy film can be improved. For example, it does not peel off even after a photoresist process for patterning the Ag film or the Ag alloy film. Furthermore, Ag having a low resistance that can be used practically (the resistance increases a little by forming an oxide film, but there is no problem in practical use), and has high reflectance or good light transmittance.
A film or Ag alloy film is obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a configuration of a laminated body according to a first embodiment of the present invention.

FIG. 2 is a schematic diagram showing a structure of a laminated body according to a second embodiment of the present invention.

FIG. 3 is a schematic diagram showing a configuration of a laminated body according to a modified example of the present invention.

FIG. 4 is a schematic diagram showing a configuration of a laminate according to another modification of the present invention.

FIG. 5 is a schematic side view of a pass film deposition type interback sputtering apparatus.

FIG. 6 is a schematic plan view of the same device.

FIG. 7 is a plan view showing a position where a peeling test is performed on the surface of the laminated body.

FIG. 8 shows a comparison result of a peeling test between a laminate having a conventional structure and a laminate of the present invention.

FIG. 9 shows the quality of the adhesion of the AgO _x film with respect to changes in the sputtering gas partial pressure.

FIG. 10 is a graph showing the relationship between the film thickness of the AgO _x film and the peeling rate.

FIG. 11: Ag alloy O for changes in sputter gas partial pressure
Indicates whether the _X film has good adhesion.

FIG. 12 is a graph showing the relationship between the film thickness of an Ag alloy O _x film and the peeling rate.

[Explanation of symbols]

1 ... Glass substrate, 2 ... AgO _X film, 3 ... Ag film,
10 ...... laminate, 12 ...... Ag alloy O _X film, 13 ...... A
g alloy film, 20 ... laminated body, 21 ... plastic substrate, 22 ... Ag-based oxide film (AgO _x film / Ag alloy O _x)
Film), 23 ... Ag-based film (Ag film / Ag alloy film), 24
...... TiO _x film / SiO ₂ film, 30 …… Sputtering device,
31 ... Sputtering room, 32 ... Carrying in / out room, 33 ... Ag
Target, 34 ... Heating part, 34a ... Heater, 35
...... Carrier, 36 ...... gate valve, 37 ...... gas inlet pipe,
40 ... vacuum pump, 41 ... power supply.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takashi Komatsu             523 Yokota, Sanmu-cho, Sanmu-gun, Chiba Prefecture             Lubac Chiba Institute for Materials Research (72) Inventor Hajime Nakamura             523 Yokota, Sanmu-cho, Sanmu-gun, Chiba Prefecture             Lubac Chiba Institute for Materials Research (72) Inventor Junya Kiyota             523 Yokota, Sanmu-cho, Sanmu-gun, Chiba Prefecture             Lubac Chiba Institute for Materials Research (72) Inventor Makoto Arai             523 Yokota, Sanmu-cho, Sanmu-gun, Chiba Prefecture             Lubac Chiba Institute for Materials Research F-term (reference) 2H042 DA04 DA11 DA12 DA15 DC02                       DE00                 3K007 CA01 CB01 CC01 DB03                 4F100 AA17C AB24B AG00A AT00A                       BA03 BA07 BA10A BA10B                       EH66B EH66C GB41 JL11                       YY00C                 4G059 AA08 AC05 AC12 DA01 DA04                       DB02 EA01 EB04 GA01 GA04                       GA14                 4K029 AA09 AA24 BA04 BA43 BB02                       BC07 BD00 BD09 CA05 CA06                       EA01

Claims (7)

[Claims] 1. A laminate having an Ag-based film, wherein an oxide film of the Ag-based material is interposed between a substrate and an Ag-based film made of an Ag-based material. 2. The laminated body having an Ag-based film according to claim 1, wherein the oxide film has a film thickness of 20 Å or more. 3. The laminate having an Ag-based film according to claim 1, wherein the base is made of a glass material. 4. A method for forming an Ag-based film, which comprises forming an Ag-based film made of an Ag-based material on a substrate, the method comprising: forming an oxide film of the Ag-based material on the substrate;
A method for forming an Ag-based film, which comprises forming the Ag-based film on the oxide film. 5. A target made of the Ag-based material is sputtered in a sputtering chamber in an atmosphere containing oxygen gas to form the oxide film on the substrate, and then the atmosphere in the sputtering chamber is kept only with an inert gas. 5. The method of forming an Ag-based film according to claim 4, wherein the target is sputtered to form the Ag-based film on the oxide film. 6. The method of forming an Ag-based film according to claim 4, wherein the oxide film has a film thickness of 20 Å or more. 7. The method for forming an Ag-based film according to claim 6, wherein the substrate is made of a glass material.