TWI694162B - Sputtering target, method for manufacturing target - Google Patents

Abstract

Provided is a sputtering target capable of forming a conductive film that does not peel off on a resin substrate without generating arc discharge.

In the sputtering target material (55) which forms an alloy thin film for a processed substrate (32) having a substrate made of resin, it contains Cu in an amount of more than 50 atomic% and more than 5 atomic% to 40 atomic% The following range contains Ni and contains 3 atomic% or more and 10 atomic% or less to contain 100 atomic% of the base material of Al, and the additive made of one or both of Zn and Mn is 0.01 atomic% or more Content rate to contain. Since the sputtering target without voids can be obtained, no arc discharge will occur.

Description

Sputtering target material and manufacturing method of target material

The present invention relates to a sputtering target material and a method of manufacturing the target material for manufacturing the sputtering target material.

Nowadays, semiconductor elements such as LSI are mounted on a mounting device where a single-layer substrate formed by forming a wiring film on a resin substrate is laminated in multiple layers. There is a demand for the technology of metal films with high adhesion. In particular, although the copper film has the advantage of low resistance, the adhesion between the resin and the resin is low. Therefore, an adhesion layer made of other metals is formed between the resin and the copper film .

The element symbol 100 in FIG. 13 is a mounting device of this prior art, and a plurality of single-layer substrates 111 ₁ and 111 ₂ are stacked.

The single-layer substrates 111 ₁ and 111 ₂ of the mounting device 100 are provided with a base 103 made of resin, and a wiring film 110 is provided on the surface of the base 103. In addition, the base 103 is provided with a connection hole 102, and inside the connection hole 102, a metal for connecting the wiring films 110 of the laminated single-layer substrates 111 ₁ and 111 _{2 to} each other is provided Bolt 119.

FIG 11 (a), is based on single layer substrate ₁₁₁₁ is attached with the uppermost layer of the single layer substrate of the base body 103 of _1112. At base 103, system 102 is provided with a coupling hole, in the bottom surface of the connection hole 102, the lower line of the substrate is exposed monolayer surface ₁₁₁₁ of the wiring film 110.

First, as shown in FIG. 11(b), a sputtering target material containing an adhesion metal such as Ti is sputtered to form the surface of the base 103 and the inner peripheral side surface of the connection hole 102 and exposed to The wiring film 110 at the bottom surface is made of an adhesion layer 118 such as a Ti thin film, and then, a sputtering target of copper is sputtered, and a seed made of a copper thin film is formed on the surface of the adhesion layer 118 Layer 115.

The patterned photoresist film is disposed on the surface of the seed layer 115, so that the seed layer 115 inside the connection hole 102 and the seed layer 115 at a specific position on the surface of the base 103 are exposed, and then immersed in the plating solution In the process, the exposed seed layer 115 is brought into contact with the plating solution, a voltage is applied between the seed layer 115 and the plating solution, and copper is deposited on the surface of the exposed seed layer 115 by electrolytic plating In order to form copper thin films 106 and 107 as shown in FIG. 11(c) inside the connection hole 102 and the surface of the base 103. In this state, the copper films 106 and 107 are in contact with the seed layer 115, the inside of the connection hole 102 is filled with the copper film 106 made of copper, and the copper films 106 and 107 are formed as the seed layer 115. thicker. The symbol 128 of the figure (c) is a photoresist film.

In this state, the adhesion layer 118 and the seed layer 115 have a portion located below the copper thin films 106 and 107, and a portion located below the photoresist film 128. After the photoresist film 128 is peeled off After exposing the seed layer 115 located below the photoresist film 128, first, it is immersed in a copper etching solution, as shown in (d) of the figure, under the copper thin films 106, 107, one side is used The seed layer 105 that has been patterned remains, the exposed seed layer 115 is etched and removed on one side, and the adhesion layer 118 is exposed at the removed portion.

Next, if it is immersed in an etching solution for etching by Ti, as shown in FIG. 13, while leaving the adhesive layer 108 positioned under the copper thin films 106 and 107 and the seed layer 105, the exposed density The coating layer 118 is removed by etching, and the base 103 is exposed at the removed portion.

By the adhesion layer 108 and the seed layer 105 and the copper film 106 in the connection hole 102, the metal plug 119 filling the connection hole 102 is formed, and by the adhesion layer 108 and the seed layer 105 and the surface of the base 103 The copper thin film 107 constitutes the wiring film 110.

The adhesion between the copper thin films 106 and 107 and the resin exposed on the surface of the substrate 103 is low, and the copper thin films 106 and 107 are easily peeled from the resin. However, since the adhesion layer 108 is a Ti film The adhesion to the resin is high and the adhesion to the seed layer 105 as a copper film is also high, therefore, the seed layer 105 and the copper films 106 and 107 are not peeled off from the base 103 .

In this case, in order to form the copper thin films 106 and 107, since Since it is necessary to form two layers of the adhesion layer 108 and the seed layer 105, the wiring film 110 has a three-layer structure, and the manufacturing engineering department will increase.

Moreover, since the adhesion layer 108 contains a large amount of elements other than Ti, such as copper, the adhesion layer 118 and the seed layer 115, which is a copper thin film, cannot be etched and etched by the same etching solution. The engineering department is complex.

Therefore, if a Cu-Ni-Al target containing nickel and aluminum is made in copper as described in Patent Document 2 below, and the Cu-Ni-Al target is sputtered to use A copper alloy film is formed on the surface of the exposed substrate of the resin, and a conductive film made of pure copper is formed on the surface of the copper alloy film as a wiring film, then the adhesion between the copper alloy film and the resin and the copper alloy The adhesion between the thin film and the conductive thin film is also good, and a wiring film that does not cause peeling from the substrate can be obtained.

However, the Cu-Ni-Al target has a large number of occurrences of arc discharge during sputtering, and therefore, the formed copper alloy thin film may become defective.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 8-332697

[Patent Literature 2] WO2014185301

The present invention was created to solve the above-mentioned problems of the prior art, and its object is to provide a sputtering target capable of forming a non-stripping wiring film on a substrate exposed without causing arc discharge, And a target manufacturing method for manufacturing the sputtering target.

After cutting the Cu-Ni-Al target and observing the inside, the inventors of the present invention discovered that a large number of voids (also referred to as "defects") occurred at the cut surface. Such voids in the sputtering target will become the cause of arc discharge. This is well known. Therefore, it is obvious that if the voids are reduced, the arc discharge will be reduced.

The present invention was created to solve such a problem, and by discovering the following knowledge, that is, when cooling and solidifying a melt containing copper, nickel and aluminum in a specific ratio, The present invention has been completed as long as one or both of Zn and Mn are contained in the melt.

That is, the invention of this case is a sputtering target material, which includes: a base material, which contains Cu, Ni, and Al, and when Cu, Ni, and Al are set to 100 atomic %, it is more than 50 atoms % More, containing Cu, and containing Ni at a content rate of 5 atomic% or more and 40 atomic% or less, and Al at a content rate of 3 atomic% or more and 10 atomic% or less; and additives are added to the foregoing In the base material, the sputtering target, its The characteristic is that the aforementioned additive is made of one or both of Zn and Mn, and is contained at a content rate of 0.01 atomic% or more with respect to 100 atomic% of the base material.

The present invention is a sputtering target in which the content of Zn and the content of Mn contained in the aforementioned additives are each set to 1.0 atomic% or less.

In addition, the present invention is a target manufacturing method, which is a target manufacturing method for manufacturing the sputtering target described above, characterized in that the solid base material and the solid additive are arranged in the same In the container, heating is performed to form a melt containing the base material and the additive, and the melt is cooled and solidified to form the sputtering target.

The wiring film formed by sputtering with less holes in the sputtering target and less arc discharge can be patterned by one etching process.

In addition, since the impedance value of the wiring film does not increase, it is possible to obtain a wiring film having a small voltage loss and not peeling off from the resin.

2‧‧‧Connecting hole

3‧‧‧Matrix

4, 5‧‧‧ alloy film

6, 7‧‧‧ conductive film

8‧‧‧Metal latch

9‧‧‧Wiring film

10‧‧‧ mounted device

55‧‧‧Sputtering target

FIG. 1 is a diagram for explaining the mounting device of the present invention.

[Fig. 2] It is used for the sputtering device used to form the mounting device. Illustrated figure.

[FIG. 3] It is a figure (1) for demonstrating the manufacturing process of the mounting apparatus of this invention.

FIG. 4 is a diagram (2) for explaining the manufacturing process of the mounting device of the present invention.

FIG. 5 is a diagram (3) for explaining the manufacturing process of the mounting device of the present invention.

FIG. 6 is a diagram (4) for explaining the manufacturing process of the mounting device of the present invention.

7 is a diagram (5) for explaining the manufacturing process of the mounting device of the present invention.

8 is a diagram (6) for explaining the manufacturing process of the mounting device of the present invention.

9 is a diagram (7) for explaining the manufacturing process of the mounting device of the present invention.

[Figure 10] is a graph of arc discharge.

[Fig. 11] (a) to (d): It is a diagram for explaining the manufacturing process of the mounted device of the prior art.

[Fig. 12] is a diagram for explaining the substrate.

[Fig. 13] is a diagram showing a prior art mounted device.

The symbol 10 in FIG. 1 represents the mounting device obtained by sputtering the target of the present invention, and the symbol 20 represents the The mounted device 10 is a motherboard that is electrically connected.

This mounting device 10 includes a support substrate 14 and first and second multilayer substrates 11 and 12 that are disposed on both sides of the support substrate 14, respectively. The first and second multilayer substrates 11 and 12 are respectively provided with A plurality of single-layer substrates 11 ₁ ~11 ₃ , 12 ₁ ~12 ₃ .

If the single-layer substrates 11 ₁ to 11 ₃ and 12 ₁ to 12 ₃ that are closer to the support substrate 14 are called the lower layer, and the further ones are called the upper layers, then each single-layer substrate 11 ₁ to 11 ₃ , At positions below 12 ₁ to 12 ₃ , other single-layer substrates 11 ₁ , 11 ₂ , 12 ₁ , 12 ₂ or the support substrate 14 are respectively arranged.

In FIG. 9, line 11 to the first multi-layer substrate of single layer substrate ₁₁₃ and the single layer portion of the substrate ₁₁₂ for display ₁₁₃ under the uppermost layer board.

The structures of the single-layer substrates 11 ₁ to 11 ₃ and 12 ₁ to 12 ₃ are the same. The single-layer substrates 11 ₁ to 11 ₃ and 12 ₁ to 12 ₃ are respectively provided with a plate-shaped base 3 and A plurality of connection holes 2 formed on the base 3, and a plurality of wiring films 9 arranged on the surface of one side of the base 3 (except the inner peripheral surface and the bottom surface of the connection hole 2), and the connection holes 2for filling metal latch 8.

The support substrate 14 is provided with a resin substrate 14a made of a resin which is an organic compound, a plurality of support substrate through holes 14b formed at the resin substrate 14a, and filling the inside of each support substrate through hole 14b Connecting body 14c and a plurality of wiring films 14d arranged on both surfaces of the resin substrate 14a. The connector 14c is provided with electrical conductivity It is electrically connected to at least one wiring film 14d.

The metal pins 8 of the single-layer substrates 11 ₁ to 11 ₃ and 12 ₁ to 12 ₃ are provided with the wiring film 9 for the wiring film 9 of the base 3 provided with the connection hole 2 where the metal pin 8 is located Make electrical connection on the surface. In FIG. 9, the connection is made at a position not shown.

In addition, the connection holes 2 of the single-layer substrates 11 ₁ to 11 ₃ and 12 ₁ to 12 _{3 are} the wiring films 9 or the support substrate 14 of the single-layer substrates 11 ₁ , 11 ₂ , 12 ₁ and 12 ₂ at the lower layer On the wiring film 14d, the metal pins 8 of each single-layer substrate 11 ₁ ~ 11 ₃ , 12 ₁ ~ 12 ₃ are connected to the wiring film 9 of the lower single-layer substrate 11 ₁ , 11 ₂ , 12 ₁ , 12 ₂ or The wiring film 14d of the support substrate 14 is electrically connected.

Therefore, the wiring films 9 of the uppermost single-layer substrates 11 ₃ and 12 ₃ of the first and second multilayer substrates 11 and 12 are respectively connected to the wiring films 14 d on one side and the other side of the support substrate 14. The wiring films 14d on both sides of the support substrate 14 are connected via the connecting body 14c. Therefore, the wiring films 9 of the uppermost single-layer substrates 11 ₃ and 12 ₃ are also electrically connected.

The motherboard 20 is provided with a motherboard body 20a and a wiring film 20b arranged on the motherboard body 20a.

At the wiring film 9 of the uppermost single-layer substrate 11 ₃ of the first multilayer substrate 11, the terminal 13 b of the semiconductor device 13 is fixed, and the wiring film 9 of the uppermost single-layer substrate 12 ₃ of the second multilayer substrate 12 Is electrically connected to the wiring film 20b of the motherboard 20 via the metal body 24.

The terminal 13b of the semiconductor device 13 is electrically connected to the integrated circuit of the semiconductor element arranged inside the semiconductor device body 13a, so the integrated circuit is connected to the host through the mounting device 10 and the metal body 24 The wiring film 20b of the board 20 is electrically connected.

If for 11 ₁ to 11 _3, the metal latches 12 ₁ to 12 _3, 8 and 9 wiring film such as described in each single layer substrates, first, the respective single layer substrates 11 ₁ to 11 _3, the base 12 ₁ to 12 ₃ 3. It is composed of a substrate made of resin or a composite material impregnated with resin in a cloth-shaped substrate woven with glass fibers.

The base 3 of FIG. 12 includes the glass fiber 26 in the resin 25. The surface of the base 3 is composed of the surface of the resin 25 and the surface of the glass fiber 26, and the resin 25 and the glass fiber 26 are exposed.

Each metal plug 8 includes an alloy thin film 4 arranged in contact with the inner peripheral surface of the connection hole 2 and a conductive film 6 arranged in contact with the surface of the alloy thin film 4. Each wiring film 9 includes an alloy thin film 5 arranged in contact with the surface of the base 3 and a conductive film 7 arranged in contact with the surface of the alloy thin film 5.

The alloy thin films 4 and 5 are on the surface of the base 3 or the inner peripheral surface of the connecting hole 2 and are in contact with the resin 25 constituting the base 3, and when the base 3 contains glass fibers 26, it is in contact with the constituent base The resin 25 of 3 and the glass fiber 26 are in contact.

The manufacturing process of the mounting device 10 described above will be described. Here, it is assumed that the second multi-layer substrate 12 has been formed on one side of the support substrate 14, and the single-layer substrate 11 other than the single-layer substrate 11 ₃ as the uppermost layer has been formed and arranged on the opposite side ₁ , 11 ₂ .

FIG. 3 shows the processed substrate 31 in this state, and on the surface, the uppermost single-layer substrate 11 _{2 of the} processed substrate 31 is exposed.

First, on the surface of the single layer substrate _112, as generally shown in Figure 4, the base body 3 attached.

The attached base body 3 may be formed with the connection hole 2 before the attachment, or the attachment hole 2 may be formed after the base body 3 is attached.

In the processing substrate 32 in this state, at the bottom surface of the connection hole 2 that becomes the uppermost substrate 3, the wiring film 9 of the single-layer substrate 11 ₂ of the next layer is exposed, and then, on the surface of the substrate 3 and the connection At the inner peripheral side and bottom of the hole 2, alloy thin films 4 and 5 are formed.

In FIG. 2, a sputtering apparatus 50 for forming alloy thin films 4 and 5 is shown.

This sputtering apparatus 50 includes a carry-in/out chamber 51a, a pre-processing chamber 51b, and a film-forming chamber 51c.

In each of the chambers 51a to 51c, vacuum exhaust devices 58a to 58c are connected to close the gate valves 59a and 59b between the chambers 51a to 51c, and the vacuum exhaust devices 58b and 58b are operated to move the front The inside of the processing chamber 51b and the film-forming chamber 51c are evacuated, and the inside of the pre-processing chamber 51b and the film-forming chamber 51c are previously formed with vacuum atmospheres, respectively.

Inside the carry-in/out chamber 51a, a conveying device 54 is arranged, and the processing substrate 32 with the base 3 exposed is carried into the carry-in/out chamber 51a and mounted on the conveying device 54.

The door of the carry-in/out room 51a is closed, the internal atmosphere is blocked from the atmosphere, the vacuum exhaust device 58a is operated, and the inside of the carry-in/out room 51a is vacuum-evacuated.

Inside the carry-in/out chamber 51a, a heating device 56 is arranged to perform vacuum exhaust while heating the processing substrate 32 arranged on the conveying device 54 by the heating device 56.

After the processing substrate 32 is heated to a specific temperature, the gate valve 59a is opened, and the processing substrate 32 is moved from the inside of the carry-in/out chamber 51a to the inside of the pre-processing chamber 51b together with the transfer device 54.

Inside the pre-processing chamber 51b, an ion gun 57 is arranged. After the gate valve 59a between the carry-in/out chamber 51a and the pre-processing chamber 51b is closed, if the rare gas is introduced from the gas introduction system (here When Ar is supplied to the ion gun 57, rare gas ions are generated inside the ion gun 57. The generated rare gas ions are discharged into the pre-processing chamber 51b.

The substrate 3 of the processing substrate 32 is exposed to the vacuum atmosphere of the pre-processing chamber 51b. If it is carried into the pre-processing chamber 51b, it is directed toward the ion gun 57 and the rare gas ion is released. The rare gas ions are irradiated onto the surface of the base 3 and the inner peripheral side surface of the connection hole 2 and the surface of the conductive film 7 of the lower single-layer substrate 111 ₂ exposed at the bottom surface of the connection hole 2 and irradiated Some are cleaned and become active.

If the ions are irradiated for a specific time, the pre-processing is completed, the gate valve 59b between it and the film-forming chamber 51c is opened, and the processed substrate 32 subjected to the pre-processing is taken together with the transport device 54 From the inside of the pre-processing chamber 51b to the inside of the film forming chamber 51c, the gate valve 59b is closed.

Inside the film forming chamber 51c, a sputtering target 55 is arranged.

The sputtering target 55 is formed by mounting a plate-shaped target alloy on the cathode electrode. The plate-shaped target alloy contains a base material including copper, nickel and aluminum, and is added to the base material Of the additives.

For this component, the base material, when the total atomic number of copper, nickel, and aluminum is set to 100 atomic %, is set to contain more than 50 atomic% of copper, and 5 atomic% or more and 40 atomic% or less It contains nickel in the range, and contains aluminum in the range of 3 atomic% or more and 10 atomic% or less, and also contains additives made of one or both of zinc and manganese.

The content rate of the additive is 0.01 atomic% or more with respect to 100 atomic% of the base material, and the content rate of zinc in the additive is 1.0 atomic% or less, and the content rate of manganese in the additive It is also set to 1.0 atomic% or less.

To explain the manufacturing process of the sputtering target 55, first, the copper raw material, the nickel raw material, the aluminum raw material, and the additive raw material, which are solid respectively, are arranged in the same melting vessel.

Copper raw materials, nickel raw materials, and aluminum raw materials are as described above. When the total atomic number of copper, nickel, and aluminum is set to 100 atomic %, it is set to contain more than 50 atomic% of copper, and 5 atoms It contains nickel in the range of% or more and 40 atom% or less, and contains aluminum in the range of 3 atom% or more and 10 atom% or less, and it is 0.01 atom% or more relative to 100 atom% of the base material. The additive system is set to 0.01 atomic% or more with respect to 100 atomic% of the base material, and the zinc content in the additive is set to 1.0 atomic% or less, and the manganese content in the additive is also set to 1.0 Atomic% or less.

The melting vessel is heated to form a melt containing copper, nickel, aluminum, and additives.

In the melt, the copper, nickel, aluminum, zinc, and manganese systems are uniformly dispersed, the melt is cooled, and the solidified material is formed into a plate shape to form a sputtering target.

If the melt is cooled, the target alloy is obtained. If the plate-shaped target alloy is fixed to the cathode electrode, the sputtering target 55 is obtained.

The composition of the molten material and the sputtering target 55 is the same as the ratio of copper, nickel, aluminum, and additives contained in the raw material containing copper, nickel, aluminum, and the raw materials of the composition.

Inside the film-forming chamber 51c, a gas release device 53 is provided, and the inside of the film-forming chamber 51c is evacuated by a vacuum exhaust device 58c, while the gas supply device 52 is used for the gas release device 53. Supply sputtering gas made of rare gas such as Ar, and then The gas discharge device 53 discharges the sputtering gas into the film forming chamber 51c, and applies a voltage to the sputtering target 55 to generate a plasma of the sputtering gas.

The surface of the substrate 3 that has been subjected to the pre-treatment is opposite to the sputtering target 55. If the surface of the sputtering target 55 is sputtered by the generated plasma, the sputtered particles are attached On the surface of the substrate 3 subjected to the pretreatment, an alloy thin film having the same content rates as the sputtering target 55 of copper, nickel, aluminum, zinc, and manganese is grown on the surface.

In the case of solidifying a molten material in which copper raw materials, nickel raw materials, aluminum raw materials, and additive raw materials are melted together, compared to melting and loading copper raw materials, nickel raw materials, and aluminum raw materials separately in different melting vessels When it was put into the same melting vessel and the raw materials of the additives were added to solidify the melt, it was found that when the raw materials were melted together, the void system was reduced.

Therefore, in the sputtering target 55 formed by melting the raw materials together and then solidifying, the voids are reduced and the frequency of arc discharge is reduced. Therefore, by sputtering the sputtering target 55, It is possible to obtain alloy thin films with few defects.

The element symbol 33 in FIG. 5 is a processed substrate formed with the alloy thin film 15 at a specific film thickness. The composition of the alloy thin film 15 is the same as the composition of the sputtering target.

The alloy film 15 is in contact with the conductive film 7 on the surface of the base 3 (excluding the inside of the connection hole 2), the inner circumferential surface of the connection hole 2 and the bottom surface of the connection hole 2, and on the bottom surface of the connection hole 2 single layer of the wiring substrate ₁₁₂ in contact with the film 9, is made electrically connected. The wiring layer ₁₁₂ of the single layer substrate film 9, by-based alloy thin film 5 and the conductive film 7 is formed.

In addition, since the uppermost alloy thin film 15 is formed on the surface irradiated with ions by the ion gun 57, the adhesion strength is higher than when the irradiation is not performed.

After forming the alloy thin film 15 at a specific film thickness, the voltage application to the sputtering target 55 and the introduction of the sputtering gas are stopped, and the sputtering is ended.

Next, the gate valves 59a and 59b are opened, and the processing substrate 33 on which the alloy thin film 15 is formed passes through the pre-processing chamber 51b and is moved into the carry-in/out chamber 51a, which becomes a vacuum atmosphere.

After closing the gate valves 59a and 59b, the gas system is introduced into the carry-in/out chamber 51a. After the inside of the carry-in/out chamber 51a becomes atmospheric pressure, the processing substrate 33 formed with the alloy thin film 15 is removed from the carry-in/out chamber 51a. take out.

Next, as shown in FIG. 6, a patterned photoresist film 28 is arranged on the surface of the alloy thin film 15.

At this photoresist film 28, an opening 29 is formed above each connection hole 2 of the uppermost substrate 3 and above a specific position of the alloy thin film 15 on the surface of the substrate 3, and between the opening 29 Under the bottom surface, the alloy thin film 15 disposed on the bottom surface and inner peripheral side surface of each connection hole 2 or the alloy thin film positioned on the surface of the base 3 are exposed 15.

The surface of the alloy thin film 15 exposed under the bottom surface of the opening 29 of the processing substrate 33 in this state will be made of a material with a copper content rate (atomic %) higher than that of the alloy thin film 15 and a lower resistivity. The film is formed in contact with the alloy thin film 15.

Regarding the specific method of forming the conductive film, for example, the treated substrate 33 in a state where the alloy thin film 15 is exposed at specific positions on the bottom surface of the opening 29 of the photoresist film 28 and the surface of the base 3 is immersed In the plating solution containing copper ions, the exposed alloy film 15 is brought into contact with the plating liquid, and then the power supply is connected to the copper electrode and the alloy film 15 immersed in the plating solution, and the power supply is activated. A voltage is applied between the alloy film 15 and the plating solution through the copper electrode, so that positive metal ions in the plating solution are attached to the portion of the alloy film 15 that is in contact with the plating liquid, to compare with the alloy film 15 A conductive film containing more copper grows, and as shown in FIG. 7, a conductive film is formed under the bottom surface of the opening 29 on the connection hole 2 and under the bottom surface of the opening 29 on the surface of the base 3 6,7的处理基地34。 The processing substrate 34 of 7.

Generally speaking, compared with the sputtering method, the growth rate in the case of the electrolytic plating method is greater, and the film thickness of the alloy thin film 15 formed by the sputtering method is by electrolytic plating The thickness of the conductive films 6 and 7 formed by the method is thicker. At the processing substrate 34, the conductive film 6 formed on the surface of the alloy thin film 15 in the connection hole 2 is used to make the inside of the connection hole 2 The upper part of the filling is located above the surface of the alloy thin film 15 on the surface of the base 3.

Next, as shown in FIG. 8, if the photoresist film 28 is peeled off, the alloy thin film 15 is exposed between the exposed portions of the conductive films 6 and 7.

The conductive film 6 inside the connection hole 2 is connected to the conductive film 7 on the surface of the base 3, but the conductive film 7 on the surface of the base 3 includes the conductive separated from each other However, in the state where the photoresist film 28 is peeled off, the internal conductive film 6 and the surface conductive film 7 are in a state of being electrically connected to each other by the alloy thin film 15.

Next, if the processed substrate 34 in this state is immersed in an etching solution for etching copper, the exposed alloy thin film 15 is etched and removed, as shown in FIG. 9, the alloy thin film 15 is removed In part, the surface of the substrate 3 positioned under the alloy thin film 15 is exposed, and the uppermost single-layer substrate 11 _{3 in} which the conductive films 6, 7 are patterned is formed.

At each of the single-layer substrates 11 ₁ to 11 ₃ and 12 ₁ to 12 ₃ , the inside of the connection hole 2 is constituted by the conductive film 6 inside the connection hole 2 and the alloy positioned under the conductive film 6 The thin film 4 is a metal plug 8 filled with a connection hole 2, and a wiring film 9 is formed on the base 3 by a conductive film 7 and an alloy thin film 5 positioned under the conductive film 7.

With respect to the resin 25 exposed on the surface of the base 3, the adhesion of the thin film of pure copper is poor.

In the present invention, the alloy films 4 and 5 in contact with the resin 25 are contained in a film material containing copper at more than 50 atomic %, As shown in the following experiment, in general, an element other than copper was included and the adhesion was measured. As a result, nickel was contained in the range of 5 atomic% or more and 30 atomic% or less, and 3 atomic% or more and 10 atoms The film material containing aluminum in the range of% or less has a higher adhesion to the resin 25 than the film of pure copper or copper oxide. As an additive, when the total atomic number of copper, nickel and aluminum is added When it is set to 100%, it includes one or both of zinc of 0.01 atomic% or more and 1.0 atomic% or less and manganese of 0.01 atomic% or more and 1.0 atomic% or less.

Regarding the additive, since there is no possibility of deteriorating the adhesion with the resin 25, and the copper content of the base material is greater than 50 atomic %, the density with the pure copper film The adhesion is also high, the metal plug 8 or the wiring film 9 will not peel off from the base 3, and because the conductive films 6, 7 are higher than the alloy thin films 4, 5 and the copper content rate is higher, Therefore, the conductive films 6 and 7 are not peeled off from the alloy thin films 4 and 5.

[Example]

When the total atomic number of copper, nickel, and aluminum is 100 atomic %, nickel is contained at 1 atomic% or more and 50 atomic% or less, and aluminum is contained at 1 atomic% or more and 10 atomic% or less, and 0.01% Containing additives made of one or both of zinc and manganese, and using the remainder as copper atoms, a test sputtering target with a composition in which the content ratio of nickel and aluminum are different is produced.

Use each sputtering target to form a glass substrate by sputtering A 50 nm alloy film in contact with the surface of the board was formed into a scraping pattern of 1 mm×1 mm×100 grid, and the adhesion evaluation by the crosscut test was conducted.

The measurement results are shown in Table 1.

In Table 1, the case where the peeling of the film due to the cross-cut test is 10 or more is described as “×”, and the case of 1 to 10 is described as “△”, and it is not observed The situation until peeling is described as "○".

From this result, it can be seen that in order to form an alloy film with high adhesion to the peeling substrate, the content of nickel is preferably 5 atomic% or more, and the content of aluminum is preferably 3 atomic% or more.

In addition, when the nickel content is greater than 40 atomic %, the hardness of the sputtering target will exceed 145Hv, so it is not ideal in workability. If it is greater than 10 atomic% Aluminum is difficult to produce sputtering target by melting method, which is not ideal.

Next, when the total atomic number of copper, nickel, and aluminum is set to 100 atomic %, copper is contained more than 50 atomic %, and 5 atomic It contains nickel in the range of% or more and 40 atom% or less, and contains aluminum in the range of 3 atom% or more and 10 atom% or less, and the base material is made such that the base material and one or both of zinc and manganese are made of additives The molten material in between is solidified to produce a sputtering target for a test with a composition of a plurality of different contents of zinc and manganese.

×10mm厚度，切斷後之剖面積係為100mm×10mm，觀察係使用染色穿透測試試驗機，空孔係對於尺寸為0.5mm

以上者進行計數。空孔數之測定結果係展示於表2中。 Each sputtering target was cut and the cross section was observed, and the number of holes was measured. The measured target is 100mm

×10mm thickness, the cross-sectional area after cutting is 100mm×10mm, the observation system uses a dye penetration tester, and the hole size is 0.5mm

Count the above. The measurement results of the number of holes are shown in Table 2.

The numerical value in Table 2 is the content rate (atomic %) of the additive when the total atomic number of copper, nickel and aluminum is set to 100 atomic %, and the number of voids is observed to be more than 3/cm ² Many sputtering targets are described as “×”, and for sputtering targets where 1 to 3 pieces/cm ² are observed, they are described as “○”, and for sputtering targets where no holes are observed , Is described as "◎".

In addition, the horizontal axis of the graph in FIG. 10 is the additive content rate (atomic %) when the total atomic number of copper, nickel, and aluminum is 100 atomic %, and the vertical axis is the measured void The number is normalized, and the relationship between the additive content and the number of holes is shown.

From the graphs in Table 2 and FIG. 10, it can be predicted that, when the total atomic number of copper, nickel, and aluminum is set to 100 atomic %, if zinc and manganese are each contained at 1.0%, the number of pores can be reduced.

Next, it contains nickel in the range of 5 atomic% or more and 40 atomic% or less, contains aluminum in the range of 3 atomic% or more and 8 atomic% or less, and contains additives in the range of 0 atomic% or more and 1.2 atomic% or less, On the other hand, the copper atom was used as the residual portion to produce a sputtering target having different additive content rates.

The additives of these sputtering targets are one of manganese and zinc, and they are different content rates in the range of 0 atomic% or more and 1.2 atomic% or less, respectively.

Each sputtering target was used to form a 50 nm-thick sputtering film on the glass substrate by sputtering, and the Cu plating film was grown to a thickness of 30 μm on this sputtering film. A scraping pattern of 1 mm×1 mm×100 grid was formed, and the evaluation of the adhesion by the crosscut test was conducted.

The measurement results are shown in the evaluation results of the respective addition amounts of Zn in Table 3 and the evaluation results of the respective addition amounts of Mn in Table 4.

According to Table 2, if one of zinc and manganese is If each contains 0.01 atomic% or more, the effect of reducing voids can be obtained, and if one or both of them are contained at 0.25 atomic% or more, the void system disappears, which is ideal.

In Table 3 and Table 4, the case where the plating film peeled off from the sputtered film due to the cross-cut test is described as “×”, and the case where it did not peel is described as “○”.

At least one of Table 3 and Table 4 is marked as "X" sputtering target, it is not available for use. Sputtering targets described as "○" in both Table 3 and Table 4 can be used.

According to Table 3 and Table 4, if the additive made of one or both of zinc and manganese is contained and formed at a content rate of 1.2 atomic% or more relative to 100 atomic% of the base material, it is And cannot be relative Since the conductive films 6, 7 formed by the Cu plating method performed in the subsequent process of sputtering film formation of the sputtering target material, good adhesion is obtained, and if it is 1.0 atomic% or less, it is possible The alloy thin films 4 and 5 with good adhesion are formed.

According to Table 3 and Table 4, it can be known that even if the aluminum content is increased, it will not affect the adhesion, but if the manufacturability of the target material by the melting method is considered, then based on As a result of the above, an additive made of one or both of zinc and manganese contains copper more than 50 atomic% when the total atomic number of copper, nickel, and aluminum is set to 100 atomic %. In the base material containing nickel in the range of at least 40 atom% or less and containing aluminum in the range of 3 atom% or more and 10 atom% or less, zinc and manganese, if one of them is based on 100 atom% of the base material When both sides are contained at a content rate of 0.01 atomic% or more and 1.0 atomic% or less and set as the sputtering target, a sputtering target with good workability and few voids can be obtained The conductive films 6, 7 formed by the Cu plating method performed in the subsequent process of sputtering film formation of the sputtering target material, and the alloy thin films 4, 5 having good adhesion, in addition, can be formed with the resin The adhesion between them is good alloy film 4, 5.

11 ₂ ‧‧‧Single layer substrate

32‧‧‧Process substrate

50‧‧‧Sputtering device

51a‧‧‧Move in and out of the room

51b‧‧‧Pre-treatment room

51c‧‧‧Film-forming room

52‧‧‧Gas supply device

53‧‧‧Gas release device

54‧‧‧Conveying device

55‧‧‧Sputtering target

56‧‧‧Heating device

57‧‧‧Ion gun

58a, 58b, 58c‧‧‧ vacuum exhaust device

59a, 59b ‧‧‧ gate valve

Claims (2)

A sputtering target material, which is a sputtering target material of Cu-Ni-Al alloy, and includes: a base material, which contains Cu, Ni and Al, and when Cu, Ni and Al are set to 100 atomic %, It contains Cu more than 50 atomic %, contains Ni at a content rate of 5 atomic% or more and 40 atomic% or less, and contains Al at a content rate of 3 atomic% or more and 10 atomic% or less; and additives, It is added to the base material. The sputtering target is characterized in that the additive is made of one or both of Zn and Mn, and is 0.01% relative to 100 atomic% of the base material. It is contained at a content rate of at least atomic %, and the content rate of Zn and the content rate of Mn contained in the aforementioned additives are each set to 1.0 atomic% or less. A target manufacturing method is a target manufacturing method for manufacturing a sputtering target as described in item 1 of the scope of patent application, characterized in that the solid base material and the solid additive are arranged in the same container In the process, heating is performed to form a melt containing the base material and the additive, and the melt is cooled and solidified to form the sputtering target.

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