JP2017071833A - High-purity copper sputtering target material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-purity copper sputtering target material capable of suppressing an abnormal discharge even by applying a high-voltage and providing a stable film deposition.SOLUTION: Cu has a purity of 99.99998 mass% or more excluding O, H, N, and C, has an Al content of 0.005 massppm or less, a Si content of 0.05 massppm or less, an Fe content of 0.02 massppm of less, a S content of 0.03 massppm or less, a Cl content of 0.1 massppm or less, an O content of 1 massppm or less, a H content of 1 massppm or less, a N content of 1 massppm or less, a C content of 1 massppm or less, and emits gas component between 50°C and 1000°C, the gas component being ionized by an electron bombardment method in a temperature desorption gas analyzer (TDS-MS) and analyzed by a quadrupole mass spectrometer to obtain a total molecular number of 5×10pcs/g or less.SELECTED DRAWING: None

Description

  The present invention relates to a high-purity copper sputtering target material used when forming a wiring film (high-purity copper film) in, for example, a semiconductor device, a flat panel display such as a liquid crystal or organic EL panel, a touch panel or the like.

Conventionally, Al is widely used as a wiring film for semiconductor devices, flat panel displays such as liquid crystal and organic EL panels, and touch panels. Recently, miniaturization (narrowing) and thinning of the wiring film have been attempted, and a wiring film having a lower specific resistance than before has been demanded.
Accordingly, with the miniaturization and thinning of the wiring film described above, a wiring film made of copper (Cu), which is a material having a specific resistance lower than that of Al, is provided.

By the way, the above-described wiring film is usually formed in a vacuum atmosphere using a sputtering target. Here, when film formation is performed using a sputtering target, abnormal discharge (arcing) may occur due to foreign matter in the sputtering target, and thus a uniform wiring film may not be formed. Here, abnormal discharge is a phenomenon in which an extremely high current suddenly and suddenly flows compared to that during normal sputtering, and an abnormally large discharge occurs suddenly. This may cause generation of particles and / or non-uniform thickness of the wiring film. Therefore, it is desirable to avoid as much as possible abnormal discharge during film formation.
Therefore, Patent Documents 1 to 5 below propose techniques for suppressing the occurrence of abnormal discharge during film formation in a pure copper sputtering target.

  Patent Document 1 proposes a sputtering target made of high-purity copper having a purity of 6N or higher. In the high purity copper sputtering target described in Patent Document 1, the contents of P, S, O, and C are each 1 ppm or less, and non-metallic inclusions having a particle size of 0.5 μm or more and 20 μm or less are 30 and 30, respectively. By setting it to 000 / g or less, foreign matter in the sputtering target is reduced, and abnormal discharge (arcing) and particles are suppressed.

  In Patent Document 2, the purity of Cu excluding O, H, N, and C is in the range of 99.999980 mass% to 99.999998 mass%, the Al content is 0.005 massppm or less, and the Si content A high-purity copper sputtering target having a mass of 0.05 massppm or less has been proposed.

  In Patent Document 3, pure copper ingot having a purity of 99.96 mass% or more is processed under predetermined conditions, so that the ratio of the total special grain boundary length Lσ to the total grain boundary length L is 25% or more. A plate (sputtering target) has been proposed. The Vickers hardness is 40 to 90, and the average crystal grain size is 10 to 120 μm.

  Patent Document 4 includes pure copper having a purity of 99.99 mass% or more, an average crystal grain size of 40 μm or less, and a total grain boundary length L and a Σ3 grain boundary length Lσ3 measured by an EBSD method. A sputtering target has been proposed in which the (Σ3 + Σ9) grain boundary length ratio (L (σ3 + σ9) / L), which is the ratio of the sum Σ9 grain boundary length Lσ9 to L (σ3 + σ9), is 28% or more.

  Patent Document 5 proposes a sputtering target in which pure copper having a purity of 99.995 mass% or more has a substantially recrystallized structure, an average crystal grain size of 80 μm or less, and a Vickers hardness of 100 or less. ing.

Japanese Patent No. 4680325 Japanese Patent Laying-Open No. 2015-034337 JP 2011-162835 A JP 2014-201814 A Japanese Patent Laid-Open No. 11-158614

Recently, in semiconductor devices, flat panel displays such as liquid crystal and organic EL panels, touch panels, etc., there has been a demand for higher density of the wiring film, which has become finer and thinner than ever before. It is necessary to form the wiring film stably. Moreover, it is necessary to load a high voltage for further high-speed film formation, and even in this case, it is required to suppress the occurrence of abnormal discharge.
Here, in the inventions described in Patent Documents 1 to 5, the abnormal discharge (arcing) cannot be sufficiently suppressed during the film formation, and the miniaturized and thinned wiring film is efficiently stabilized. And could not be formed.

  The present invention has been made in view of the above-described circumstances, and provides a high-purity copper sputtering target material that can suppress the occurrence of abnormal discharge even when a high voltage is applied and can stably form a film. The purpose is to do.

In order to solve the above-described problems, the high-purity copper sputtering target material of the present invention has a Cu purity excluding O, H, N, and C of 99.99998 mass% or more and an Al content of 0.005 massppm. Hereinafter, the Si content is 0.05 massppm or less, the Fe content is 0.02 massppm or less, the S content is 0.03 massppm or less, the Cl content is 0.1 massppm or less, the O content is 1 massppm or less, The H content is 1 massppm or less, the N content is 1 massppm or less, and the C content is 1 massppm or less, and is 1 × 10 ⁻⁷ Pa or less by a temperature programmed desorption gas analyzer (TDS-MS). Gas components released between 50 ° C and 1000 ° C by heating a sample collected from the target material in an ultra-high vacuum , Ionized by electron bombardment, and wherein the total number of molecules of the generated ions quadrupole mass spectrometer with a release gas obtained by composition analysis is 5 × 10 ¹⁷ cells / g or less.

  In the high-purity copper sputtering target material having this configuration, the purity of Cu excluding O, H, N, and C is 99.99998 mass% or more, the Al content is 0.005 massppm or less, and the Si content is 0. .05 massppm or less, Fe content is 0.02 massppm or less, S content is 0.03 massppm or less, Cl content is 0.1 massppm or less, O content is 1 massppm or less, H content is 1 massppm or less, Since the N content is 1 massppm or less and the C content is 1 massppm or less, the generation of foreign substances such as oxides, carbides, nitrides, sulfides and chlorides in the sputtering target can be suppressed. The occurrence of the abnormal discharge caused can be suppressed. Furthermore, generation of gas during film formation can be suppressed and the degree of vacuum can be maintained, and film formation can be performed stably.

Further, the sample collected from the target material is heated in an ultrahigh vacuum of 1 × 10 ⁻⁷ Pa or less of TDS-MS, and the total number of molecules of the released gas released between 50 ° C. and 1000 ° C. is 5 × 10 ¹⁷ / g or less, so the amount of gas released into the Ar gas atmosphere from the target during sputtering is small, so the generation of secondary electrons during sputtering becomes stable, and abnormal discharge occurs. Can be suppressed. As the effluent gas described above, for example _{H 2, O 2, H 2} O, CO, CO 2 , and the like.

Here, in the high purity copper sputtering target material of this invention, it is preferable that the average crystal grain diameter shall be 70 micrometers or less.
Since the sputtering rate varies depending on the crystal orientation, when the sputtering progresses, unevenness occurs on the sputtering surface due to the above-described difference in sputtering rate. If the grain size of the crystal grains on the sputter surface is large, the unevenness becomes large, and charges are concentrated on the convex portion, so that abnormal discharge is likely to occur. Therefore, it is possible to further suppress the occurrence of abnormal discharge by limiting the average crystal grain size on the sputtering surface to 70 μm or less.

Moreover, in the high purity copper sputtering target material of this invention, it is preferable that Vickers hardness shall be in the range of 35-55Hv.
In this case, since the Vickers hardness of the sputter surface is limited to 55 Hv or less, the internal strain in the crystal grains is small, the secondary electrons are uniformly emitted during sputtering, and the film is stably formed. Can do. Further, by reducing the internal strain, the sputtering rate becomes uniform, and it is possible to suppress the formation of irregularities on the sputtering surface when the sputtering progresses, and the occurrence of abnormal discharge can be suppressed.
On the other hand, since the Vickers hardness of the sputtered surface is 35 Hv or more, the crystal grain size can be made relatively small, and it is possible to suppress the formation of irregularities on the sputtered surface when the sputtering proceeds, and abnormal discharge Can be suppressed.

  ADVANTAGE OF THE INVENTION According to this invention, even when a high voltage is loaded, generation | occurrence | production of abnormal discharge can be suppressed and the high purity copper sputtering target material which can form into a film stably can be provided.

Below, the high purity copper sputtering target material which concerns on one Embodiment of this invention is demonstrated.
The high-purity copper sputtering target material according to this embodiment is used when a high-purity copper film used as a wiring film in a semiconductor device, a flat panel display such as a liquid crystal or organic EL panel, a touch panel, etc. is formed on a substrate. It is what

  The composition of the high-purity copper sputtering target material according to the present embodiment is such that the purity of Cu excluding O, H, N, and C is 99.99999 mass% or more, the Al content is 0.005 massppm or less, Si Content of 0.05 massppm or less, Fe content of 0.02 massppm or less, S content of 0.03 massppm or less, Cl content of 0.1 massppm or less, O content of 1 massppm or less, H content The amount is 1 massppm or less, the N content is 1 massppm or less, and the C content is 1 massppm or less.

In addition, in the high purity copper sputtering target material according to the present embodiment, a predetermined size is increased from the target material in an ultrahigh vacuum of 1 × 10 ⁻⁷ Pa or less by a temperature programmed desorption gas analyzer (TDS-MS). The sample collected was heated, the gas component released between 50 ° C. and 1000 ° C. was ionized by the electron impact method, and the generated ions were analyzed by composition analysis with a quadrupole mass spectrometer. The total number of released gases such as ₂ , O ₂ , H ₂ O, CO, and CO ₂ is set to 5 × 10 ¹⁷ pieces / g or less.

Furthermore, in the high purity copper sputtering target material according to the present embodiment, the average crystal grain size is 70 μm or less, and the Vickers hardness is in the range of 35 to 55 Hv.
The reason why the composition of the high purity copper sputtering target material according to the present embodiment, the number of released gas molecules, the average crystal grain size, and the Vickers hardness are defined as described above will be described below.

(Cu: 99.99998 mass% or more)
When forming a wiring film (high-purity copper film) by sputtering, it is preferable to reduce impurities as much as possible in order to suppress abnormal discharge (arcing). Here, if the purity of Cu is 99.99998 mass% or more, it is not necessary to carry out the purification process more than necessary, and it is possible to suppress a significant increase in manufacturing cost.

(Al: 0.005 massppm or less)
Since Al is an element that easily forms oxides, carbides, nitrides, and the like, it tends to remain as foreign matter in the sputtering target. Therefore, by limiting the Al content to 0.005 mass ppm or less, it is possible to suppress the occurrence of abnormal discharge (arcing) during film formation even when the purity of Cu is 99.99998 mass% or more. .

(Si: 0.05 massppm or less)
Since Si is an element that easily forms oxides, carbides, nitrides, and the like, it tends to remain as foreign matter in the sputtering target. Therefore, by limiting the Si content to 0.05 mass ppm or less, even when the purity of Cu is 99.99998 mass% or more, it is possible to suppress the occurrence of abnormal discharge (arcing) during film formation. .

(Fe: 0.02 massppm or less)
Fe is an element that tends to form oxides, carbides, nitrides, and the like as compared with copper, and therefore tends to remain as foreign matter in a high-purity copper sputtering target. Therefore, by limiting the Fe content to 0.02 mass ppm or less, it is possible to suppress the occurrence of abnormal discharge (arcing) during film formation even if the purity of Cu is 99.99998 mass% or more. .

(S: 0.03 massppm or less)
S is an element that reacts with other impurity elements to form sulfides and is likely to remain as foreign matter in the sputtering target. Further, if it exists alone, it may be gasified and ionized during film formation, lowering the degree of vacuum, and causing abnormal discharge (arcing). From the above, in this embodiment, the S content is limited to 0.03 massppm or less.

(Cl: 0.1 mass ppm or less)
Cl is an element that reacts with other impurity elements to form chlorides and tends to remain as a foreign substance in the sputtering target. Further, if it exists alone, it may be gasified and ionized during film formation, lowering the degree of vacuum, and causing abnormal discharge (arcing). From the above, in this embodiment, the Cl content is limited to 0.1 mass ppm or less.

(O, H, N: each 1 ppm or less)
When forming a film with a sputtering target, since it is carried out in a vacuum atmosphere, if these gas components are present in a large amount, the degree of vacuum may be lowered during film formation and abnormal discharge (arcing) may be induced. Moreover, there is a possibility that particles are generated by abnormal discharge and the quality of the high purity copper film is deteriorated. From the above, in this embodiment, the contents of O, H, and N are limited to 1 massppm or less, respectively.

(C: 1 massppm or less)
C reacts with other impurity elements to form carbides, and tends to remain as foreign matter in the sputtering target. Moreover, since C tends to remain in the sputtering target as a single substance, there is a possibility that abnormal discharge (arcing) may be induced. From the above, in this embodiment, the C content is limited to 1 massppm or less.

In the present embodiment, as described above, the upper limit of the content of various impurity elements is set, but the purity of Cu excluding O, H, N, and C is 99.99998 mass% or more. Thus, it is necessary to regulate the total amount of impurity elements.
Here, analysis of impurity elements excluding O, H, N, and C can be performed using a glow discharge mass spectrometer (GD-MS).
The analysis of O can be carried out by an inert gas melting-infrared absorption method, the analysis of H and N can be carried out by an inert gas melting-heat conduction method, and the analysis of C can be carried out by a combustion-infrared absorption method.

(The total number of molecules in the released gas is 5 × 10 ¹⁷ / g or less)
If there are many strains in the crystal grains, defects in the crystal grains increase, and the gas dissolved in the copper diffuses to the target surface through the defects, and the gas is released during the sputtering. The generation of secondary electrons becomes unstable. Therefore, a sample collected to a predetermined size from the target material is heated in an ultrahigh vacuum of TDS-MS of 1 × 10 ⁻⁷ Pa or less, and H ₂ , O released between 50 ° C. and 1000 ° C. _When the total number of released gases such as ₂ , H ₂ O, CO, and CO ₂ exceeds 5 × 10 ¹⁷ / g, the amount of gas released into the Ar atmosphere is large. The generation of secondary electrons may become unstable.
Therefore, in the present embodiment, the total number of molecules of the released gas such as H ₂ , O ₂ , H ₂ O, CO, CO ₂ released from the sample collected to a predetermined size from the target material is 5 × 10 5. By setting the number to ¹⁷ atoms / g or less, it is possible to reduce the amount of gas released to the Ar gas atmosphere and stabilize the generation state of secondary electrons during sputtering.
In order to reliably stabilize the generation state of secondary electrons during sputtering, the total number of molecules of the emitted gas such as H ₂ , O ₂ , H ₂ O, CO, CO ₂ is 4 × 10 ^17. It is preferable to set it to not more than pieces / g.

(Average crystal grain size: 70 μm or less)
Since the sputtering rate varies depending on the crystal orientation, when the sputtering proceeds, irregularities corresponding to the crystal grains are generated on the sputtering surface due to the above-described difference in the sputtering rate.
Here, when the average crystal grain size exceeds 70 μm, the unevenness generated on the sputter surface becomes large, and charges are concentrated on the convex part, so that abnormal discharge is likely to occur.
For this reason, in the high purity copper sputtering target of this embodiment, the average crystal grain size is defined as 70 μm or less.
In addition, in order to suppress irregularities on the sputtering surface when sputtering proceeds and to reliably suppress abnormal discharge, the average crystal grain size is preferably 60 μm or less, and more preferably 50 μm or less.

(Vickers hardness: 35Hv to 55Hv)
In the high-purity copper sputtering target according to the present embodiment, when the Vickers hardness exceeds 55 Hv, the internal strain in the crystal grains becomes large, and the generation state of secondary electrons at the time of sputtering becomes unstable. May not be performed stably. Further, the sputtering rate becomes non-uniform due to the internal strain, and the sputter surface is uneven, which may increase the number of micro arc discharges. On the other hand, when the Vickers hardness is less than 35 Hv, the crystal grain size becomes coarse, so that when the sputtering proceeds, irregularities on the sputtering surface occur, and abnormal discharge is likely to occur.
For this reason, in the present embodiment, the Vickers hardness is defined within a range of 35 Hv to 55 Hv.
In order to suppress coarsening by suppressing the coarsening of the crystal grain size, the lower limit of the Vickers hardness is preferably 37 Hv or more, and more preferably 39 Hv or more. Further, in order to make the sputtering rate uniform and reliably suppress film thickness variation and micro arc discharge, the upper limit of Vickers hardness on the sputtering surface is preferably 53 Hv or less, and more preferably 50 Hv or less. .

Next, the manufacturing method of the high purity copper sputtering target material which is this embodiment is demonstrated.
First, electrolytic copper having a copper purity of 99.99 mass% or more is prepared, and this is electrolytically purified. The above-described electrolytic copper is used as an anode, a titanium plate is used as a cathode, and the anode and the cathode are immersed in an electrolytic solution for electrolysis. Here, the electrolytic solution is prepared by diluting the reagent copper nitrate with water and further adding hydrochloric acid. Thus, by adding hydrochloric acid to the copper nitrate electrolyte, generation of nitrous acid gas can be suppressed, and the amount of impurities in the electrodeposited copper can be reduced (see Patent No. 3102177). By performing such electrolytic purification, high-purity copper in which the purity of Cu excluding O, H, N, and C is 99.99998 mass% or more can be obtained.

  In this embodiment, the contents of Al, Si, and Fe in the anode (electro-copper) used in the electrolytic purification process are each defined as 1 mass ppm or less, and further, the contents of Al, Si, and Fe in the electrolyte are included. Each amount is specified to be 1 massppm or less. The cleanliness of the room where the electrolytic purification is performed is set to 10000 or less. By performing electrolytic purification under such conditions, the Al content can be 0.005 massppm or less, the Si content can be 0.05 massppm or less, and the Fe content can be 0.02 massppm or less.

  In the present embodiment, a nitric acid-based electrolytic solution is used to reduce S during electrolytic purification. In the electrolyte, impurities such as S are contained in glue and organic polymer added to smooth the cathode surface, and when these are taken into the cathode, the S concentration in the cathode increases. . Therefore, in this embodiment, a synthetic polymer such as a mixture of polyethylene glycol and polyvinyl alcohol having a low S content is used in combination with the nitric acid-based electrolyte as an additive.

Further, Cl, O, H, and N are dissolved in a high vacuum of 10 ⁻⁴ Pa or less, thereby volatilizing as a gas in the vacuum and being reduced to a predetermined concentration.
Although the solubility of C increases in Cu when the melting temperature is raised, if the melting temperature is kept low, it becomes possible to keep it at a predetermined concentration or less even when dissolved in a high-purity graphite container. Specifically, a predetermined C concentration can be maintained by melting at 1150 ° C. or lower.

  As described above, the purity of Cu excluding O, H, N, and C is set to be 99.99998 mass% or more, the Al content is 0.005 massppm or less, the Si content is 0.05 massppm or less, The content is 0.02 massppm or less, the S content is 0.03 massppm or less, the Cl content is 0.1 massppm or less, the O content is 1 massppm or less, the H content is 1 massppm or less, and the N content is 1 massppm. Hereinafter, high purity copper having a C content of 1 mass ppm or less can be obtained.

Next, this high-purity copper is used as a melting raw material and melted in a vacuum melting furnace to produce a high-purity copper ingot.
Hot forging is performed on the obtained high-purity copper ingot in a temperature range of 450 to 700 ° C. Thereby, the cast structure is destroyed and adjusted to a structure having equiaxed crystal grains. Next, hot rolling is performed in a temperature range of 450 to 700 ° C. to obtain a predetermined shape.

  Next, cold working is performed on the hot-rolled material described above. Here, in order to reduce the strain in the crystal grains and reduce the defects in the crystal grains while being fine and uniform, it is effective to increase the rolling reduction during cold rolling. By doing so, recrystallization easily occurs in the subsequent heat treatment after the cold working, the distortion in the crystal grains is small, the defects in the crystal grains are reduced, and the amount of gas released during sputtering is reduced. For this reason, it is preferable that the rolling reduction in one rolling pass is in the range of 15% to 25%. Furthermore, the rolling rate in the entire rolling is preferably 40% or more.

Next, a recrystallization heat treatment is performed on the cold-worked material. The heat treatment temperature is preferably 350 ° C. or higher and 450 ° C. or lower, and the holding time is preferably 1 hour or longer and 2 hours or shorter.
Note that the number of molecules of released gas such as H ₂ , O ₂ , H ₂ O, CO, and CO ₂ released from a sample collected to a predetermined size from the target material by repeating cold working and heat treatment multiple times. You may adjust so that it may become 5 * 10 < ¹⁷ > piece / g or less.

  As described above, the high purity copper sputtering target material according to this embodiment is manufactured.

According to the high-purity copper sputtering target material of the present embodiment configured as described above, the purity of Cu excluding O, H, N, and C is set to 99.99998 mass% or more. Can be manufactured at a relatively low cost.
In addition, the content of Al, which is an element that easily forms oxides, carbides, nitrides, sulfides, chlorides, etc. and remains as foreign substances, is 0.005 massppm or less, the Si content is 0.05 massppm or less, Fe The content is 0.02 massppm or less, the S content is 0.03 massppm or less, the Cl content is 0.1 massppm or less, the O content is 1 massppm or less, the H content is 1 massppm or less, and the N content is 1 massppm. Hereinafter, since the C content is 1 mass ppm or less, the generation of foreign matter in the sputtering target can be suppressed, and the occurrence of abnormal discharge due to the foreign matter can be suppressed.
Furthermore, since the contents of S, Cl, O, H, and N that cause gas generation during film formation are regulated as described above, the degree of vacuum can be maintained, and film formation can be performed stably. Can be implemented.

Moreover, in the high purity copper sputtering target material which is this embodiment, the sample extract | collected to the predetermined magnitude | size from the target material is heated in the ultrahigh vacuum of 1 * 10 <^-7> Pa or less of TDS-MS, and 50 Since the total number of molecules of released gas such as H ₂ , O ₂ , H ₂ O, CO, CO ₂ etc. released between 0 ° C. and 1000 ° C. is 5 × 10 ¹⁷ / g or less, sputtering The amount of released gas in the inside is small, the generation state of secondary electrons during sputtering is stabilized, and the occurrence of abnormal discharge can be suppressed.

  Further, in the high purity copper sputtering target material according to the present embodiment, the average crystal grain size is set to 70 μm or less, so that the case where irregularities corresponding to the crystal grains were formed on the sputtering surface due to the progress of sputtering. However, the unevenness does not increase, and the occurrence of abnormal discharge can be further suppressed.

Furthermore, in the high-purity copper sputtering target material of this embodiment, since the Vickers hardness is 35 Hv or more, the crystal grain size can be made relatively small, and the sputtering progresses so that the crystal grain is formed on the sputtering surface. Even when unevenness corresponding to the above is formed, the occurrence of abnormal discharge can be suppressed.
Further, since the Vickers hardness is 55 Hv or less, the internal strain in the crystal grains is small, the secondary electrons are uniformly emitted during sputtering, and the sputtering film formation can be performed stably. In addition, it is possible to prevent the sputtering rate from becoming non-uniform due to internal strain, to suppress the formation of large irregularities on the sputtering surface due to the progress of sputtering, and to suppress the occurrence of abnormal discharge.

As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the technical idea of the invention.
In this embodiment, the sputtering target for forming a high-purity copper film as the wiring film has been described as an example. However, the present invention is not limited to this, and even when a high-purity copper film is used for other purposes. Can be applied.
Moreover, about a manufacturing method, it is not limited to this embodiment, The thing manufactured with the other manufacturing method may be used.

  Below, the result of the evaluation test evaluated about the high purity copper sputtering target material which is this embodiment mentioned above is demonstrated.

(Invention Examples 1 to 7)
Electrolytic purification conditions exemplified in the embodiment using electrolytic copper as a raw material with Al being 1 massppm or less, Si being 1 massppm or less, Fe being 1 massppm or less, and other impurities (excluding O, H, N, and C) being 20 massppm or less. The copper raw material was manufactured by performing electrolytic purification in
The raw material produced by the above production method was put in a crucible made of high-purity carbon and melted under vacuum (pressure 10 ⁻⁵ Pa) at 1130 ° C. Then, it poured into the mold produced with high purity carbon in the vacuum state (pressure 10 < ^-5 > Pa), and produced the high purity copper ingot of diameter 150mm x height 200mm.

The obtained high purity ingot was hot forged at 500 ° C. and then hot rolled at 500 ° C.
Next, the hot-rolled material was cold-rolled at a reduction rate of 20% to obtain a cold-rolled plate having a thickness of 10 mm. The rolling rate at this time was 95%.
Next, the cold-worked material was heat-treated at a temperature of 400 ° C. and a holding time of 1.5 hours.
Then, it cut out to 125 mm in diameter and 5 mm in thickness, was used as a high purity sputtering target material, and HIP joined with the backing plate of Cr-Zr-Cu (C18150).

(Invention Example 8)
Electrolytic purification conditions exemplified in the embodiment using electrolytic copper as a raw material with Al being 1 massppm or less, Si being 1 massppm or less, Fe being 1 massppm or less, and other impurities (excluding O, H, N, and C) being 20 massppm or less. The copper raw material was manufactured by performing electrolytic purification in
The raw material produced by the above production method was put in a crucible made of high-purity carbon and melted under vacuum (pressure 10 ⁻⁵ Pa) at 1130 ° C. Then, it poured into the mold produced with high purity carbon in the vacuum state (pressure 10 < ^-5 > Pa), and produced the high purity copper ingot of diameter 150mm x height 200mm.

The obtained high purity ingot was hot forged at 500 ° C. and then hot rolled at 500 ° C.
Next, the hot forged material was cold-rolled at a reduction rate of 20%. The rolling rate at this time was 80%.
Next, the cold-worked material was heat-treated at a temperature of 500 ° C. and a holding time of 2 hours.
Then, it cut out to 125 mm in diameter and 5 mm in thickness, was used as a high purity sputtering target material, and HIP joined with the backing plate of Cr-Zr-Cu (C18150).

(Invention Example 9)
Electrolytic purification conditions exemplified in the embodiment using electrolytic copper as a raw material with Al being 1 massppm or less, Si being 1 massppm or less, Fe being 1 massppm or less, and other impurities (excluding O, H, N, and C) being 20 massppm or less. The copper raw material was manufactured by performing electrolytic purification in
The raw material produced by the above production method was put in a crucible made of high-purity carbon and melted under vacuum (pressure 10 ⁻⁵ Pa) at 1130 ° C. Then, it poured into the mold produced with high purity carbon in the vacuum state (pressure 10 < ^-5 > Pa), and produced the high purity copper ingot of diameter 150mm x height 200mm.

The obtained high purity ingot was hot forged at 500 ° C. and then hot rolled at 500 ° C.
Next, the hot-rolled material was cold-rolled at a reduction rate of 20%. The rolling rate at this time was 95%.
Next, the cold-worked material was heat-treated at a temperature of 350 ° C. and a holding time of 1 hour.
Then, it cut out to 125 mm in diameter and 5 mm in thickness, was used as a high purity sputtering target material, and HIP joined with the backing plate of Cr-Zr-Cu (C18150).

(Comparative example)
In Comparative Example 1, electrolysis was performed without adding chlorine to the electrolytic solution, and electrolysis was performed in a general room instead of a clean room. Ordinary glue and ethylene glycol were used as additives for smoothing the cathode. Melting casting was performed at 1300 ° C. using a high-purity graphite crucible in a nitrogen atmosphere and atmospheric pressure. The obtained ingot (diameter 150 mm × height 200 mm) was hot-forged at 500 ° C. to break the cast structure to be equiaxed, then hot-rolled at 500 ° C., and then a reduction rate of 5%. And then heat-treated at 400 ° C. for 1 hour. The rolling rate at this time was 40%.

  In Comparative Example 2, electrolytic purification was performed in a general room, and electrolysis was performed using glue and ethylene glycol as additives. Moreover, it melt | dissolved at 1300 degreeC in the vacuum using the high purity graphite crucible. The obtained ingot (same shape) was similarly hot-forged at 500 ° C. to break the cast structure to be equiaxed, then hot-rolled, and then cold-rolled at a reduction rate of 8%, 350 A heat treatment was held at 1 ° C. for 1 hour. The rolling rate at this time was 75%.

  In Comparative Example 3, electrolytic purification was performed in a general room, and polyethylene glycol and polyvinyl alcohol were used as additives during electrolysis. It melt | dissolved at 1150 degreeC using the high purity graphite crucible by the atmospheric pressure of nitrogen atmosphere instead of vacuum melting. The obtained ingot was similarly forged and hot-rolled, then cold-rolled at a reduction rate of 10%, and heat-treated at 500 ° C. for 1 hour. The rolling rate at this time was 60%.

  In the comparative example 4, it melt | dissolved at atmospheric pressure in nitrogen atmosphere, and melt | dissolved at 1300 degreeC using the graphite crucible. The obtained ingot was hot forged at 500 ° C., hot rolled at 500 ° C., then cold rolled at a rolling rate of 10%, and heat-treated at 300 ° C. for 1 hour. The rolling rate at this time was 60%.

  About the obtained sputtering target material, the following procedures evaluated the component composition (amount of impurities), the amount of gas released by TDS, the average crystal grain size, the Vickers hardness, and the number of abnormal discharges. The evaluation results are shown in Tables 1 and 2.

(Amount of impurities)
The analysis of impurity elements excluding O, H, N, and C was carried out using a glow discharge mass spectrometer (VG-9000 type manufactured by VG Elemental). The analysis procedure was performed according to ASTM.
The analysis of O was performed by an inert gas melting-infrared absorption method (JIS H 1067). Specifically, analysis was performed according to JIS Z 2613 using TCEN600 manufactured by LECO.
Analysis of H was performed by an inert gas melting-heat conduction method. Specifically, analysis was performed according to JIS Z 2614 using RHEN602 manufactured by LECO.
The analysis of N was performed by an inert gas melting-heat conduction method. Specifically, the analysis was performed using TCEN600 manufactured by LECO.
Analysis of C was performed by a combustion-infrared absorption method. Specifically, the analysis was performed according to JIS Z 2615 using CSLS600 manufactured by LECO.

(Gas release amount)
A sample was taken from the target material, the surface of the sample was polished with # 400 to # 600 emery polishing paper, ultrasonically washed with alcohol and then dried with a drier, and a gas release amount was measured. The weight of the sample was 250 to 400 mg, and the thickness was 1 to 2 mm. The emission gas was measured by TDS-MS (WA1000S / W type) manufactured by Electronic Science Co., Ltd.
The above-mentioned sample was heated in an ultrahigh vacuum of 1 × 10 ⁻⁷ Pa or less. The rate of temperature increase was 60 ° C./min. Between 200 ° C. and 1000 ° C., 30 ° C./min. It was. The scan width at the time of analysis was 1 to 200 amu. The measurement temperature range was 50 ° C to 1000 ° C.

(Average crystal grain size)
The average crystal grain size was measured based on JIS H 0501: 1986 (cutting method) by observing the microstructure on the rolled surface (ND surface) using an optical microscope.

(Vickers hardness)
The hardness of the sample was measured with a Macro Vickers hardness tester according to JIS Z 2244 on the surface used as a target.

(Abnormal discharge)
The sputtering method was a DC magnetron sputtering method. A target to be sputtered was attached to the cathode in the chamber, and the vacuum was drawn so that the ultimate vacuum was 5 × 10 ⁻⁴ Pa or less. First, in order to remove dirt and processing flaws on the target processed surface, the sputter power was gradually increased to perform pre-sputtering, and the sputter power was increased to 3000 W. Note that the power of the pre-sputtering was 660 Wh.
Subsequently, discharging and stopping for 1 minute were repeated at a sputtering power of 3000 W and a sputtering pressure of 0.4 Pa until the sputtering power reached 10 kWh. Then, the number of abnormal discharges that occurred during the discharge was measured with a micro arc monitor (MAM Genesis) manufactured by Landmark Technology.

In Comparative Example 1, the amount of impurities was large, the purity of copper was out of the scope of the present invention, the number of released gas molecules was also out of the scope of the present invention, and the number of abnormal discharges was as high as 660.
In Comparative Example 2, the content of Al, Si, Fe, S was outside the scope of the present invention, the number of molecules of the released gas was also outside the scope of the present invention, and the number of abnormal discharges was as high as 820.
In Comparative Example 3, the contents of Cl, O, H, and N were out of the scope of the present invention, the number of released gas molecules was also out of the scope of the present invention, and the number of abnormal discharges was as high as 755.
In Comparative Example 4, the contents of Cl, O, H, N, and C are outside the scope of the present invention, the number of molecules of the released gas is also outside the scope of the present invention, and the number of abnormal discharges is as high as 950. It was.

On the other hand, in the example of the present invention in which the purity of copper, the amount of impurities, and the number of molecules of released gas are within the scope of the present invention, the number of abnormal discharges was 250 or less.
From the above, according to the example of the present invention, it is possible to provide a high-purity copper sputtering target material that can suppress the occurrence of abnormal discharge even when a high voltage is applied and can stably form a film. confirmed.

Claims (3)

The purity of Cu excluding O, H, N, and C is 99.99999 mass% or more, the Al content is 0.005 massppm or less, the Si content is 0.05 massppm or less, and the Fe content is 0.02 massppm. Hereinafter, S content is 0.03 massppm or less, Cl content is 0.1 massppm or less, O content is 1 massppm or less, H content is 1 massppm or less, N content is 1 massppm or less, C content Is 1 massppm or less,
A gas sampled from the target material is heated in an ultra-high vacuum of 1 × 10 ⁻⁷ Pa or less by a temperature programmed desorption gas analyzer (TDS-MS) and released between 50 ° C. and 1000 ° C. The component is ionized by an electron impact method, and the total number of molecules of the released gas obtained by analyzing the composition of the generated ions with a quadrupole mass spectrometer is 5 × 10 ¹⁷ molecules / g or less. High purity copper sputtering target material.   2. The high-purity copper sputtering target material according to claim 1, wherein an average crystal grain size is 70 μm or less.   The high-purity copper sputtering target material according to claim 1 or 2, wherein the Vickers hardness is in a range of 35 to 50 Hv.