KR20030020986A - Sputtering target - Google Patents

Abstract

The present invention relates to materials comprising new titanium that can be used to form a titanium alloy sputtering target. The titanium alloy sputtering target may be sputtered in a sputtering atmosphere containing nitrogen to form an alloy TiN thin film, or in a nitrogen-containing and oxygen-containing sputtering atmosphere to form an alloy TiON thin film. The thin film formed according to the present invention may have a barrier layer property comparable to that of TaN as a thin film applied to a Cu barrier, a non-columnar grain structure, low electrical resistivity, high chemical stability. In addition, the titanium alloy sputtering target made in accordance with the present invention is more cost effective compared to high purity tantalum materials when applied to semiconductors and has excellent mechanical strength suitable for the application of high strength sputtering.

Description

Sputtering Target {SPUTTERING TARGET}

Integrated circuit technology is changing from aluminum subtractive process to copper dual damascene process. The shift from the alloy of aluminum and aluminum to the alloy of copper and copper is due to the new barrier layer material developed, in particular TaN. TiN thin films used in aluminum technology can be formed by sputtering a titanium target well in a sputtering gas atmosphere including, for example, nitrogen. TiN films are known to be inferior barrier layers to copper compared to TaN because of the very high diffusion rate of copper atoms through the TiN films.

The problems associated with the TiN barrier layer are depicted in FIGS. 1 and 2. In particular, FIG. 1 shows the preferred barrier layer structure and FIG. 2 shows the problems associated with the TiN barrier layer.

First, referring to FIG. 1, a semiconductor wafer piece 10 is shown. The wafer piece 10 comprises a substrate 12, which may for example comprise monocrystalline silicon. To assist in the interpretation of the following claims, the terms "semiconductive substrate" and "semiconductor substrate" refer to semiconducting materials and semiconducting material layers (assemblies comprising one or other materials). It is defined as meaning any structure consisting of. The semiconducting material includes, but is not limited to, a bulk semiconducting material such as a semiconducting wafer (an aggregate comprising one or more other materials thereon). The term " substrate " refers to any supporting structure, including but not limited to the semiconductor substrate described above.

The insulating layer 14 is formed on the substrate 12. The insulating layer 14 may include, for example, silicon dioxide or borophosphosilicate glass (BPSG). Layer 14 may also comprise silicon fluoride dioxide having a dielectric constant of 3.7 or less, or a so-called "low-k" dielectric material. In a particular embodiment, layer 14 may comprise an insulating material having a dielectric constant of 3.0 or less.

Barrier layer 16 extends to a trench in insulating material 14 and a copper containing seed layer 18 is formed over barrier layer 16. The copper containing seed layer 18 may be formed, for example, by sputter deposition from a high purity copper target. The term "high purity" refers to a target having a purity of at least 99.995% (ie, 4N5 purity). Copper-containing material 20 is formed over copper-containing seed layer 18 and may be formed over seed layer 18 by, for example, electrochemical deposition. The copper-containing material 20 and the seed layer 18 may both be referred to as a copper-based layer or a copper-based mass.

Barrier layer 16 is provided to prevent copper diffusion from materials 18 and 20 to insulating material 14. It is reported that the titanium material of the prior art is not suitable as a barrier layer for preventing the diffusion of copper. Problems related to materials comprising titanium of the prior art are depicted in FIG. 2. FIG. 2 shows the structure 10 of FIG. 1, but is modified to show certain problems that may occur if pure titanium or titanium nitride is used as the barrier layer 16. In particular, FIG. 2 shows channels 22 extending through barrier layer 16. Channel 22 may result from columnar grain growth associated with the titanium material of barrier layer 16. Channel 22 effectively provides a path for copper diffusion to insulating layer 14 through barrier layer 16 comprising titanium. The columnar grain growth may occur during the formation of the Ti or TiN layer 16 or during the high temperature process after the deposition. In particular, it has been found that even when the titanium material of the prior art was deposited without columnar grains, the material could fail at temperatures above 450 ° C.

In an effort to avoid the problems described in FIG. 2, it has been developed that a barrier material other than titanium is used as the diffusion layer 16. Among the materials developed is tantalum nitride (TaN). TaN was found to have good chemical stability as barrier layer and grain structure close to nanometer size to prevent copper diffusion. However, there is a problem that the price of tantalum is too expensive to economically use the TaN layer in the semiconductor manufacturing process. In addition, we have found that many titanium alloys can have superior mechanical properties over tantalum in both sputtering targets and sputtered thin films. Therefore, the titanium alloy is suitable for applications where high performance is required.

Titanium alloys are less expensive than tantalum. Therefore, if a method of using a titanium-containing material instead of a tantalum-based material as a barrier layer for suppressing copper diffusion can be developed, the microelectronics industry for the use of copper-related technology can be developed. It is possible to reduce the material cost. Therefore, it is desirable to develop a material comprising new titanium that is suitable as a barrier layer to prevent or inhibit copper diffusion. The material containing titanium may be of any purity, but is preferably a material of high purity. The term "high purity" refers to a target having a purity of at least 99.95% (ie, 3N5 purity).

The present invention relates to a titanium alloy thin film having improved copper diffusion barrier properties. The present invention also relates to a titanium alloy sputtering target and additionally to a method of suppressing copper diffusion to a substrate.

Preferred embodiments of the present invention are described below with reference to the following drawings.

1 is a schematic cross-sectional view of a prior art semiconductor wafer piece showing a conductive copper material separated from an insulating layer by a barrier layer.

FIG. 2 is a drawing of the prior art wafer fragment of FIG. 1 showing problems that may occur when using prior art Ti containing materials as barrier layers.

3 is a schematic cross sectional view of a semiconductor wafer piece in a preliminary step of the method of the present invention.

FIG. 4 is a drawing of the wafer slice of FIG. 3 as seen in the process steps following the wafer slice of FIG.

FIG. 5 is a diagram of the FIG. 3 wafer slice seen in the process steps following the wafer slice of FIG.

FIG. 6 is a drawing of the FIG. 3 wafer slice seen in the process steps following the wafer slice of FIG.

7 is a partially enlarged view of the wafer slice of FIG. 5.

FIG. 8 is a schematic graph showing the relative concentration of material “Q” with respect to the copper containing layer, TiQ layer and SiO layer along the axis shown in FIG. 4.

FIG. 9 is a schematic graph of the relative concentrations of material "Q" with respect to the copper containing layer, TiQ layer and SiO layer along the axis shown in FIG.

10 is a chart showing the improvement of the mechanical properties of Ti-Zr alloy compared to Ta in the prior art.

11 is a schematic cross-sectional view of a conventional sputtering target structure.

12 is a graph showing the Rutherford Back-scattering Spectroscopy (RBS) profile of deposited Ti _0.45 Zr _0.024 N _0.52 .

FIG. 13 shows sheet resistance of Ti _0.45 Zr _0.024 N _0.52 . Rs spacing is equal to 1/3 sigma, and the gradient shown is 68.99; 67.88; 66.76; 65.65; 64.54; 63.42; 62.31; 61.19; And 60.08.

FIG. 14 is a graph showing the Rutherford Back-scattering Spectroscopy profile of Ti _0.45 Zr _0.024 N _0.52 after vacuum annealing at 450-700 ° C. for 1 hour.

FIG. 15 is a graph showing a Rutherford Back-scattering Spectroscopy profile of a TiZrN thin film after stripping the Cu layer from the wafer. The Cu layer present in the TiZrN thin film and the initial portion of the structure was formed according to the conventional method of the present invention. After 5 hours at 700 ° C., the data shown do not show any diffusion of Cu into the TiZrN layer.

The invention described herein relates to a material comprising new titanium that can be used to form a titanium alloy sputtering target. These sputtering targets can be used in place of targets comprising tantalum due to their high strength and resulting thin film properties. In detail, in some embodiments, the titanium alloy sputtering target may be used to form a barrier layer for the application of Cu. The titanium alloy sputtering target may be sputtered by reacting well in a sputtering gas atmosphere including nitrogen for forming a titanium alloy nitride thin film, or in an atmosphere containing oxygen and containing nitrogen for forming a titanium alloy oxygen nitrogen thin film. . The thin films formed according to the present invention may have a barrier layer property comparable to the non-columnar grain structure, low electrical resistivity, high chemical stability and barrier layer property of TaN. In addition, the titanium alloy sputtering target material produced according to the present invention is more cost effective in semiconductor applications than high purity tantalum materials.

In one aspect, the present invention includes a sputtering target comprising Ti and one or more alloying elements having a standard electrode potential of less than -1.0V. In the range where Zr, Al or Si are present, it may be desirable that they do not exist in the form of Ti and binary alloys (with binary composites consisting of TiZr, TiAl and TiSi). In addition, if the target comprises a binary alloy of TiZr, it may be desirable for Zr to be present in the range of 32-38 atomic% or in the range of 12-18 atomic%. Or in the application of a Cu barrier, it is preferred that Zr be present in any amount of 0-50% by weight. In an embodiment in which the sputtering target includes a plurality of alloying elements, all of the alloying elements have a standard electrode potential of less than -1.0 V, or all of the alloying elements have a standard electrode potential of less than -1.0 V. It may not.

In another aspect, the present invention includes a method of inhibiting copper diffusion to a substrate. A first layer comprising titanium and one or more alloying elements having a standard electrode potential of less than -1.0 V is formed on the substrate. A layer based on copper is then formed over the first layer and separated from the substrate by the first layer. The first layer inhibits copper diffusion from the copper based layer to the substrate.

However, in another aspect, the present invention includes a sputtering target comprising Ti and one or more elements having a melting temperature of 2400 ° C. or higher. In an embodiment in which the sputtering target includes a plurality of alloy elements in addition to Ti, all of the elements other than Ti have a melting temperature of 2400 ° C. or higher, or all of the elements other than Ti have a melting temperature of 2400 ° C. or higher. It may not.

In another aspect, however, the present invention comprises a sputtering target comprising Ti and one or more alloying elements having an atomic radius difference of at least 8%, or at least 10% compared to Ti and at least 20% in some applications. It includes. In embodiments in which the sputtering target comprises a plurality of alloying elements, all of the alloying elements have an atomic radius difference of at least 8% compared to Ti, or all of the alloying elements have at least 8% of Ti as compared to Ti. It may not have an atomic radius difference.

For the purpose of interpreting this specification and the claims that follow, "Ti-based" materials are defined as materials in which titanium is the most element, and "alloying element" is the most common in certain materials. It is defined as an element that is not an element of. A "majority element" is defined as an element present at a higher concentration than other elements of the material. The major element is the predominant element in the material, but may also be less than 50% in the material. For example, if titanium is 30% and no other element has a concentration above 30%, titanium is the main element of the material. Other elements with concentrations below 30% become "alloying elements". The titanium based materials depicted here will often contain alloying elements in concentrations of 0.001-50 atomic percent. The percentages and concentrations referred to herein are atomic percent and atomic concentration, and of course, this is not the case when specifying concentrations and percentages other than atomic percent or atomic concentration.

In addition, for the purpose of interpreting the following specification and claims, "copper-based material" is defined as a material in which copper is a major element.

A typical embodiment of the present invention is depicted in Figures 3-9. 3, a semiconductor wafer piece 50 is shown. The wafer piece 50 comprises a semiconducting material substrate 52, such as, for example, single crystal silicon. An insulating material 54 is formed over the substrate 52, and openings 56 are formed in the insulating material 54. Materials 52 and 54 comprise the same material, respectively, as depicted in prior art materials 12 and 14. For example, the hole 56 may comprise a trench for the formation of copper in a dual damascene process.

Referring to FIG. 4, barrier layer 58 is formed over insulating layer 54 and in hole 56. According to the invention, the barrier layer 58 comprises titanium and is intended to prevent diffusion from the copper-based layer formed next to the insulating material 54. In one aspect of the invention, barrier layer 58 is a standard electrode potential (more specifically, Cl ⁻¹ / Cl reference eledtrode) of less than ^−1.0 V (ie, more negative than −1.0 V) with titanium. It consists of one or more elements with a standard reduction potential measured with Although in certain embodiments the elements may not comprise Al, Si or Zr, suitable elements are Al, Ba, Be, Ca, Ce, Cs, Hf, La, Mg, Nd, Sc, Sr, Y, Mn , V, Si and Zr. In addition, barrier layer 58 may consist of one or more elements having a standard electrode potential of less than about -1.0 V with titanium, or one or more elements having a standard electrode potential of less than -1.0 V of titanium. have. In addition, barrier layer 58 may comprise one or both of nitrogen and oxygen in addition to one or more elements having a standard electrode potential of less than Ti and -1.0V. Layer 58 may be considered a thin film formed over substrate 54, in particular embodiments may have a thickness of about 2-500 nm, in detail may have a thickness of about 2-50 nm, or about It may have a thickness of 2-20 nm.

In another aspect of the invention, barrier layer 58 comprises titanium and one or more elements having a melting temperature of about 2400 ° C. or greater. Suitable elements can be selected from the group consisting of Nb, Mo, Ta and W. In addition, the barrier layer 58 may be composed of one or more elements having a melting temperature of titanium and about 2400 ° C. or higher, or may be composed of one or more elements having a melting temperature of titanium and about 2400 ° C. or higher. In addition, barrier layer 58 may comprise one or two of nitrogen or oxygen in addition to Ti and one or more elements having a melting temperature of about 2400 ° C. or higher. Layer 58 may be considered a thin film formed over substrate 54, and in certain embodiments will have a thickness of about 2-50 nm, and in particular may have a thickness of about 2-20 nm. The elements having a melting temperature of about 2400 ° C. or higher can stabilize the titanium alloy due to the refractory properties of the elements.

In one aspect of the invention, it is important for the material to maintain the desired small grain size in the barrier layer, and the sputtering target of the present invention is characterized in that the elements contained in the target comprising titanium comprise 8% of the atomic size of titanium Or more, and preferably at least 10%, or more preferably at least 20%, having different atomic sizes. This difference in atomic size confuses the titanium lattice structure, thus preventing grain growth in the lattice. The degree of difference in grain size between titanium and the other elements included in barrier layer 58 will result in an amount of disruption of the lattice, and thus can affect the amount of grain size occurring at various temperatures. Therefore, it is preferable to use elements having a large difference in size from titanium rather than atoms having a small difference in size from titanium. Groups of elements with an atomic radius difference of at least 8% compared to titanium are Mn, Fe, Co, Ni and Y, and groups of elements with an atomic radius difference of at least 20% compared to titanium are Be, B, C , La, Ce, Pr, P, S, Nd, Sm, Si, Gd, Dy, Ho, Er and Yb. Some of the elements having an atomic radius difference of more than 8% or more than 20% compared with titanium partially coincide with those having a standard electrode potential of less than -1.0 V, and some are not. The present invention involves the use of elements with an atomic radius difference of greater than 8% (or in some applications greater than 20%) in comparison with titanium to form a barrier layer, so that titanium, Si, P, Sputtering target comprising at least one of S, Sc, Mn, Fe, Co, Ni, Y, Be, B, C, Mo, La, Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er and Yb It is made, including.

In a sense, the invention includes alloying elements that fall into three categories: standard electrode potential of less than about −1.0 V; A melting temperature of at least about 2400 ° C .; Or atomic size that differs by more than 8% from the atomic size of titanium. Table 1 shows various exemplary elements that may fall into one or more of the three categories. Table 1 does not show all suitable elements within one or more of the three categories.

element Atomic radius Atomic Radius Difference from Ti (2.00 kPa) (%) Standard electrode potential (V) (reaction) Melting Point (℃) Al 1.82 -9 -1.70 (Al ³⁺ / Al) 660 B 1.17 -41.5 -1.20 (B ³⁺ / B) 2300 Ba 2.78 39 -3.53 (Ba ²⁺ / Ba) 725 Be 1.4 -30 -1.80 (Be ²⁺ / Be) 1278 C 0.91 -54.5 0.14 (C ⁴⁺ / C) 3500 Ca 2.23 11.5 -3.26 (Ca ²⁺ / Ca) 839 Ce 2.7 35 -2.82 (Ce ³⁺ / Ce) 795 Co 1.67 -16.5 -0.88 (Co ²⁺ / Co) 1495 Cr 1.85 -7.5 -1.37 (Cr ²⁺ / Cr) 1857 Cs 3.34 67 -3.44 (Cs ¹⁺ / CS) 28.5 Dy 2.49 24.5 -2.27 (Dy ³⁺ / Dy) 1412 Er 2.45 22.5 -2.51 (Er ³⁺ / Er) 1522 Fe 1.72 -14 -1.10 (Fe ²⁺ / Fe) 1535 Gd 2.54 27 -2.67 (Gd ³⁺ / Gd) 1311 Ho 2.47 23.5 -2.58 (Ho ³⁺ / Ho) 1470 Hf 2.16 8 -2.24 (Hf ⁴⁺ / Hf) 2150 La 2.74 37 -2.85 (La ³⁺ / La) 920 Mn 1.79 -10.5 -1.79 (Mn ²⁺ / Mn) 1245 Mo 2.01 0.5 -0.63 (Mo ⁴⁺ / Mo) 2617 Nb 2.08 4 -0.94 (Nb ⁵⁺ / Nb) 2468 Nd 2.64 32 -2.73 (Nd ³⁺ / Nd) 1010 Ni 1.62 -19 -0.67 (Ni ²⁺ / Ni) 1453 P 1.23 -38.5 -0.74 (P ³⁺ / P) 44 Pr 2.67 33.5 -2.82 (Pr ³⁺ / Pr) 935 S 1.09 -45.5 -0.11 (S ²⁺ / S) 113 Sc 2.09 4.5 -2.34 (Sc ³⁺ / Sc) 1539 Si 1.46 -27 -1.09 (Si ²⁺ / Si) 1410 Sm 2.59 29.5 -3.42 (Sm ²⁺ / Sm) 1072 Ta 2.09 4.5 -1.07 (Ta ⁵⁺ / Ta) 2996 V 1.92 -4 -1.7 (V ²⁺ / V) 1890 W 2.02 One -0.69 (W ²⁺ / W) 3410 Y 2.27 13.5 -2.6 (Y ⁴⁺ / Y) 1523 Yb 2.4 20 - 824 Zr 2.16 8 -1.65 (Zr ²⁺ / Zr) 1852 Standard electrode potentials, in particular standard reduction potentials, were measured using Cl ⁻¹ / Cl reference electrodes.

In an exemplary process, layer 58 is a barrier layer to prevent diffusion from conductive copper based material to insulating material 54. In such embodiments, it may be desirable for the barrier layer 58 to be conductive to provide additional electron flow beyond that provided by the conductive copper based layer. In the above embodiment, it may be preferable that the barrier layer 58 has an electrical resistivity of 300 µΩ · cm or less.

An exemplary method of forming the barrier layer 58 is to sputter the deposition layer 58 from a target consisting of titanium and one or more elements. The one or more elements may have a standard electrode potential of less than about −1.0 V, an atomic radius size difference of at least 8% compared to Ti, and / or a melting temperature of 2400 ° C. or more. In a particular embodiment, the target comprises titanium and one or more elements having a standard electrode potential of less than about −1.0 V, an atomic radius size difference of at least 8% compared to Ti, and / or a melting temperature of at least 2400 ° C. Can be. The invention also includes a target consisting of titanium and one or more elements having a standard electrode potential of less than about −1.0 V, a difference in atomic radius size of at least 8% compared to Ti and / or a melting temperature of 2400 ° C. or higher. It includes an embodiment that is made.

Exemplary targets are 0.001-50 atomic% with at least 50 atomic% titanium, a standard electrode potential of less than about -1.0 V, an atomic radius size difference of at least 8% compared to Ti and / or a melting temperature of 2400 ° C. or higher. It may comprise one or more elements. In another embodiment, the target has at least 90 atomic percent titanium, a standard electrode potential of less than -1.0 V, an atomic radius size difference of at least 8% compared to Ti and / or a melting temperature of at least 2400 ° C. It may comprise one or more elements of atomic%.

Although previous targets have been produced by titanium and other applications with one or more of Nb, Al, Si, W and Zr (eg, other than for diffusion barriers), the targets of the present invention are that they are copper It is used for the barrier and can also be distinguished from the previous target in that the concentrations of Nb, W, and Zr may differ from the previous target and the target of the present invention. For example, the alloy of the present invention may include titanium as the main element, Nb, W or Zr as an additional element (in the range of 32 to 38 atomic% and 12 to 18 atomic% in the case of Zr, in the case of Nb) 6-8 atomic% range, and in the case of W, except 35 to 50 atomic% range. In addition, targets comprising prior art titanium may be used for the novel method of the present invention for forming a copper barrier layer.

Targets using the method of the present invention may be sputtered in an atmosphere such that only the target material is deposited on the thin film 58, or alternatively the material from the atmosphere may be combined with the materials from the target. And sputtered in an atmosphere to be deposited on 58). For example, to form a barrier layer 58 comprising nitrogen from the target in addition to the materials, the target may be sputtered in an atmosphere comprising nitrogen containing components. Exemplary nitrogenous components are biatomic nitrogen (N ₂ ). The deposited thin film has a standard electrode potential of less than −1.0 V, an atomic radius size difference of at least 8% compared to Ti, and / or a melting temperature of 2400 ° C. or more, and labels at least one element included as the target. Can be referred to by stoichiometry Ti _x Q _y N _z with " Q " In a particular process, the material Ti _x Q _y N _z may comprise x = 0.1-0.7, y = 0.001-0.3 and z = 0.1-0.6.

Another exemplary method of forming the barrier layer 58 is that both the component comprising nitrogen and the component comprising oxygen are present in the barrier layer 58 to include both nitrogen and oxygen, and titanium and titanium are included. Sputtering the deposition layer from the target consisting of one or more components except. The process can form a barrier layer with stoichiometric Ti _x Q _y N _z O _w . Q again represents elements having an atomic radius size difference of at least 8% compared to Ti, elements comprising a standard electrode potential of less than about −1.0 V, and / or elements having a melting temperature of 2400 ° C. or higher. . For example, the compound Ti _x Q _y N _z O _w may comprise x = 0.1-0.7, y = 0.001-0.3, z = 0.1-0.6 and w = 0.0001-0.0010. For example, the oxygen-containing component used to form the Ti _x Q _y N _z O _w may be O ₂ .

Introducing nitrogen and / or oxygen into barrier layer 58 may be advantageous in that it may improve the high temperature stability of the barrier layer as compared to its ability to block copper diffusion at high temperatures. For example, the nitrogen and / or oxygen may interfere with the Ti columnar grain structure, thus forming a more equiaxed grain structure.

Hereinafter, a specific method for forming a sputtering target and depositing a thin film from the sputtering target according to the present invention will be described with reference to Examples 1-4.

The barrier layer 58 formed in accordance with the present invention may comprise an average grain size of 100 nm or less, and in certain processes, preferably comprise an average grain size of 10 nm or less. More preferably, the barrier layer may comprise an average grain size of less than 1 nm. In addition, the barrier layer material has sufficient stability so that the average grain size can be maintained at 100 nm or less, and in certain embodiments the thin film is exposed at 500 ° C. for 30 minutes in a vacuum annealing, and then at 10 nm or 1 nm or less. Can be.

The small average grain size of the thin film 58 of the present invention makes it possible to provide a thin film which better prevents copper diffusion as compared to the titanium-containing thin film of the prior art. In detail, the titanium-containing thin film of the prior art often forms a large grain size in a process of 450 ° C. or more, and thus may have columnar-type defects shown in FIG. 2. The process of the present invention can prevent the formation of such defects, thus making it possible to form a titanium-containing diffusion layer better than in the prior art processes.

4, a copper-containing seed layer 60 is formed on the barrier layer 58. For example, the copper containing seed layer 60 may comprise high purity copper (ie, at least 99.995% pure copper) and may be deposited, for example, by sputter deposition from a high purity copper target.

FIG. 5 shows a wafer piece 50 after chemical-mechanical polishing to remove layers 58 and 60 from above the top surface of insulating material 54, leaving materials 58 and 60 in trench 56. ). In addition, FIG. 5 shows a process that can occur specifically when elements with a standard electrode potential of less than -1.0 V are in layer 58, and a region with elements of higher concentration than other regions of material 58. FIG. To form 62, layer 58 is exposed to a thermal process that causes diffusion of elements with a standard electrode potential of less than -1.0V. Suitable thermal processes that can cause such migration of elements with standard electrode potentials below −1.0 V include annealing for about 30 minutes at a temperature of about 500 ° C. under vacuum.

FIG. 7 shows an enlarged view of the area of the wafer piece 50 of FIG. 5 and shows the area 62 more clearly. In addition, FIG. 7 shows that another region 64 having elements having a standard electrode potential of less than −1.0 V of increased concentration may be formed adjacent to the copper-based layer 60. Region 64 is not shown in FIG. 5 due to space limitations in the figures. It will be appreciated that region 64 may be effectively removed in certain processes of the present invention, depending on the elements introduced into barrier layer 58.

8 and 9 graphically illustrate aspects of the invention that elements having a standard electrode potential of less than −1.0 V may migrate into barrier layer 58 during high temperature annealing.

Referring first to FIG. 8, this shows the concentration of elements having a standard electrode potential of less than −1.0 V for the copper layer 60, the TiQ layer 58, and the SiO layer 54, represented by “Q”, and in detail “ Graph of the relative percentage of Q "). TiQ and SiO are not intended to be a stoichiometric representation of any of the materials of barrier layer 58 or insulating material 54, but rather merely distinguish layers 58 and 64 from the diagram of FIG. For example, a material referred to as "SiO" may generally be SiO ₂ ). The graph of FIG. 8 is shown along the axis shown in FIG. 4 and thus corresponds to the process step before annealing of FIG. 5.

FIG. 9 shows a graph similar to the graph of FIG. 8, but shows a graph along the axis of FIG. 5, thus showing the relative concentration after annealing of FIG. 5. 9 shows that the concentration of Q is increased at the interface between the TiQ layer 58 and the SiO layer 54 compared to the concentration throughout the middle region of TiQ. 9 also shows that the concentration of Q can be increased at the interface between the copper based layer 60 and the TiQ layer 58.

Although the insulating layer 54 is specified as an SiO layer in FIGS. 8 and 9, the SiO is an exemplary composition for the insulating layer 54, and the present invention is an embodiment in which the layer 54 includes other insulating materials. It can be understood to include. In addition, the relative concentration of Q shown in FIG. 9 is for illustrative purposes only, and it may be understood that FIG. 9 shows a qualitative representation rather than a quantitative representation of the concentration of Q.

The advantage of using elements with standard electrode potentials below −1.0 V is supported by FIGS. 7, 8 and 9. In particular, these elements will tend to diffuse into the interface region of the barrier layer 58 during annealing. Thus, the element can form regions 62 and 64 of FIG. 7 having an improved copper barrier state compared to the remaining central region of layer 58. In addition, the region 62 may have improved properties for bonding the layer 58 to the insulating material 54. Thus, the barrier layer formed in accordance with the present invention can adhere better to the insulating material than the barrier layer formed according to the prior art, thus alleviating some problems associated with the barrier layer of the prior art.

FIG. 6 shows the wafer piece 50 in the process step subsequent to FIG. 5, in particular showing the material 70 based on copper formed in the trench 56 (FIG. 5). For example, copper-based material 70 may be formed by copper electrodeposition over seed layer 60. An advantage of the conductive barrier layer 58 is shown in FIG. 6. In detail, as the trench becomes smaller and smaller, the amount of the trench smaller by the barrier layer 58 may increase as compared with the amount consumed by the copper material 70. Thus, layers 58, 60 and 70 can be considered as conductive components with layer 58 having a larger volume as the size of the trench becomes smaller. Layer 58 has an increasingly larger volume because there is a limit to the thickness of layer 58 required to maintain proper copper diffusion barrier properties. As the relative volume of the layer 58 increases in the conductive component comprising layers 58, 60 and 70, good conductive properties in the material 58 to maintain good conductive properties in the conductive component. It may be required to have

Materials formed in accordance with the present invention may have suitable mechanical properties for use in a sputtering target. FIG. 10 shows that materials formed in accordance with the present invention may have mechanical properties equivalent to or greater than those of 3N5 tantalum having the mechanical properties of FIG. 10 reported in Ksi units (eg, 1000 lbs / in ² ). Shows.

Example

The invention is illustrated by, but not limited to, the following examples. The embodiments present an exemplary method for forming a sputtering target comprising various materials that can be included by the present invention. The sputtering target may have a variety of shapes, including exemplary shapes of the so-called ENDURA ™ target type available from Honeywell Electronics, Inc. An exemplary ENDURA ™ target structure 200 includes a backing plate 202 and a target 204, shown in FIG. 11. The target structure 200 is shown in cross-section in FIG. 11 and, if viewed from above, typically comprises a rounded outer surface. Although the target structure 200 is shown to comprise a backing plate 202 supporting the target 204, the present invention also provides a monolithic target structure (e.g., the entire structure is a target). Material) and other planar target structures.

Example 1

The TiY target contains 1.0 atomic% of Y, a reaction element having a standard electrode potential of -2.6 V and an atomic radius of 13.5% larger than the atomic radius of Ti. During vacuum skull melting, a predetermined amount of 3N (99.9%) purity of Y was added to Ti of 5N (99.999%) purity. After a uniform alloy was formed, the alloy was injected into a graphite mold to form a billet. The billets were forged and rolled using conventional thermal processing processes and made into sputtering targets. The Ti-5 atomic% Y target reacts well in an N ₂ / Ar atmosphere with 4 different (0, 5, 10, 15scm) N ₂ flows and the sum of the chamber pressures is 4 × 10 ⁻³ mTorr. By sputtering. The resulting TiYN thin film had a thickness of approximately 20 nm and an electrical resistivity in the range of approximately 130-300 µΩ · cm, and included a very small grain size that could not be measured by X-ray and was microcrystalline or amorphous.

Example 2

The TiTa target has a melting point of 2996 ° C. and contains 0.65 atomic% of Ta which is a reaction element having a standard electrode potential of −1.07 V. During vacuum skull melting, a predetermined amount of Ta of 3N5 (99.95%) purity was added to Ti of 5N (99.999%) purity. After a uniform alloy was formed, the alloy was injected into a graphite mold to form a billet. The billets were forged and rolled using conventional thermal processing processes and made of sputtering targets. The Ti-0.65 atomic% Ta target reacts well in an N ₂ / Ar atmosphere with 4 different (0, 5, 10, 15scm) N ₂ flows and the total of chamber pressures is 4 × 10 ⁻³ mTorr. By sputtering. The resulting TiTaN thin film had a thickness of approximately 20 nm and an electrical resistivity in the range of approximately 130-250 µΩ · cm, and included a very small grain size that could not be measured by X-rays and was microcrystalline or amorphous.

Example 3

The TiZr target comprises 5.0 atomic% Zr, a reaction element having a standard electrode potential of -1.65 V. During vacuum skull melting, a predetermined amount of Zr of 2N8 (99.8%) purity was added to Ti of 5N (99.999%) purity. After a uniform alloy was formed, the alloy was injected into a graphite crucible to form a billet. The billets were forged and rolled using conventional thermal processing processes and made of sputtering targets. The Ti-5 atomic% Zr target sputtered well in a N ₂ / Ar atmosphere. The resultant TiZrN thin film had a thickness of approximately 20 nm and an electrical resistivity of approximately 125 µΩ · cm. FIG. 13 shows sheet resistance of the sputtered TiZrN thin film. The TiZrN thin film had a very small grain size that could not be measured by X-rays and was stable after vacuum annealing at 700 ° C. for 5 hours, which is microcrystalline or amorphous. Then, a 150 nm Cu thin film was deposited on the TiZrN thin film, and the diffusion characteristics of the TiZrN thin film could be tested after annealing at a high temperature. The result is that the TiZrN thin film has good adhesion with intermetallic dielectrics and good wetting characteristics with Cu. The thin film eventually had properties suitable for a typical Cu / low-k dielectric process. FIG. 12 shows the Rutherford Back-scattering Spectroscopy (RBS) profile of Ti _0.45 Zr _0.024 N _0.52 deposited, and Table 2 shows various situations of FIG. 12 data. 14 shows no apparent diffusion of Cu into the TiZrN layer after vacuum annealing at about 450-700 ° C. for 1 hour. 15 shows the RBS profile of the TiZrN thin film after the Cu layer is removed from the wafer. This figure again shows no significant diffusion of Cu into the TiZrN layer after 5 hours at 700 ° C.

Thin film composition (atomic%) measured by RBS pellicle Thickness (nm) Si O Ti N Zr TiZrN 20 0 0 0.45 0.526 0.024 SiO ₂ 300 0.334 0.666 0 0 0 Si wafer One 0 0 0 0

Example 4

The TiAl target contains 1.0 atomic% Al, which is a reaction element having a standard electrode potential of -1.70 V. During vacuum skull melting, a predetermined amount of Al of 3N5 (99.95%) purity was added to Ti of 5N (99.999%) purity. After a uniform alloy was formed, the alloy was injected into a graphite mold to form a billet. The billets were forged and rolled using conventional thermal processing processes and made into sputtering targets. The Ti-1.0 atomic% Al target was sputtered well in an N ₂ / Ar atmosphere with a total of four different N ₂ flows (0, 5, 10, 15 sccm) and a chamber pressure of 4 × 10 ⁻³ mTorr. . The resulting TiAlN thin film had a thickness of approximately 20 nm, an electrical resistivity in the range of approximately 130-300 µΩ · cm, and included a very small grain size, which could not be measured by X-ray and was either microcrystalline or amorphous.

The embodiments described herein are exemplary embodiments, and it is to be understood that the present invention also includes embodiments other than those specifically described above. For example, the chemical-mechanical polishing described as occurring between the steps of FIGS. 4 and 5 may instead be done after electrodeposition of the copper material 70 shown in FIG. 6. Also, as used to form the region 62, the annealing described in FIG. 5 may instead be done after the process of FIG. In addition, although various aspects of the invention have been described with respect to forming barrier layers to mitigate copper diffusion, the methods described herein retard the diffusion of metals other than copper, such as Ag or Al. Or may be used for the purpose of forming a barrier layer that inhibits.

Claims (184)

A sputtering composition consisting of Ti and one or more alloying elements that do not comprise Al having a standard electrode potential of less than about -1.0 V, wherein the sputtering composition is used to form a barrier layer for a copper-containing material. The sputtering composition of claim 1, wherein the copper-containing material is a copper-based material. The sputtering composition of claim 1 comprising at least one alloying element that does not have a standard electrode potential of less than about -1.0V. 2. The sputtering composition of claim 1, wherein the alloying elements in the sputtering composition are elements having a standard electrode potential of less than about -1.0V. The method of claim 1, wherein the one or more alloying elements are Be, B, Si, Ca, Sc, V, Cr, Mn, Fe, Sr, Y, Zr, Cs, Ba, La, Hf, Ta, Ce, Pr, A sputtering composition, characterized in that it is selected from the group consisting of Nd, Sm, Gd, Dy, Ho and Er. The sputtering composition of claim 1, wherein the one or more alloying elements are selected from the group consisting of Be, Ca, Sr and Ba. The sputtering composition of claim 1, wherein the one or more alloying elements comprise Zr. The sputtering composition of claim 1, wherein the one or more alloying elements comprise B. The sputtering composition of claim 1, wherein the one or more alloying elements comprise Hf. The sputtering composition of claim 1, wherein the one or more alloying elements comprise V. The sputtering composition of claim 1, wherein the one or more alloying elements comprise Cr. The sputtering composition of claim 1, wherein the one or more alloying elements comprise Mn. The sputtering composition of claim 1, wherein the one or more alloying elements comprise Fe. A sputtering target comprising Ti and one or more alloying elements that do not comprise Al having an atomic radius difference of at least 8% relative to titanium, wherein the sputtering target is used to form a barrier layer for a Cu-containing material. 15. The sputtering target of claim 14, wherein the one or more alloying elements are selected from the group consisting of Ca, Mn, Fe, Co, Ni, Y, Zr and Hf. 15. The sputtering target of claim 14, wherein the one or more alloying elements comprise Co. 15. The sputtering target of claim 14, wherein the one or more alloying elements comprise Ni. 15. The sputtering target of claim 14, wherein the one or more alloying elements comprise Y. A sputtering target comprising Ti and one or more alloying elements having an atomic radius difference of at least 20% relative to titanium and used to form a barrier layer for Cu-containing material. 20. The group of claim 19, wherein the one or more alloying elements are Be, B, C, Si, P, S, Cs, Ba, La, Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er, and Yb. A sputtering target, characterized in that selected from. 20. The sputtering target of claim 19, wherein the one or more alloying elements are selected from the group consisting of Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er and Yb. 20. The sputtering target of claim 19, wherein the one or more alloying elements comprise Ba. 20. The sputtering target of claim 19, wherein the one or more alloying elements comprise La. 20. The sputtering target of claim 19, wherein the one or more alloying elements comprise Yb. A sputtering composition comprising Ti and Zr and containing less than 12 atomic percent Zr. The sputtering composition of claim 25 containing less than 8 atomic percent Zr. The sputtering composition of claim 25 containing less than 6 atomic percent Zr. The sputtering composition of claim 25 containing less than 2 atomic percent Zr. The sputtering composition of claim 25 containing 2-12 atomic percent Zr. Ti and one or more alloying elements having a standard electrode potential of less than about −1.0 V; Does not include TiAl alloys or TiSi binary alloys; And a sputtering target that does not include a TiZr binary alloy in which Zr in the range of 12-18 atomic% or 32-38 atomic% is present. The method of claim 30, wherein the one or more alloying elements are Be, B, Ca, Sc, V, Cr, Mn, Fe, Sr, Y, Cs, Ba, La, Hf, Ta, Ce, Pr, Nd, Sm, A sputtering target, characterized in that selected from the group consisting of Gd, Dy, Ho and Er. 31. The sputtering target of claim 30, wherein the one or more alloying elements are selected from the group consisting of Be, Ca, Sr and Ba. 31. The sputtering target of claim 30, wherein the one or more alloying elements comprise B. 31. The sputtering target of claim 30, wherein the one or more alloying elements comprise Hf. 31. The sputtering target of claim 30, wherein the one or more alloying elements comprise V. 31. The sputtering target of claim 30, wherein the one or more alloying elements comprise Cr. 31. The sputtering target of claim 30, wherein the one or more alloying elements comprise Mn. 31. The sputtering target of claim 30, wherein the one or more alloying elements comprise Fe. Ti and one or more alloying elements having an atomic radius difference of at least 8% relative to titanium; Does not include binary complexes consisting of Ti and alloying elements selected from the group consisting of Al and Si; And a sputtering target that does not contain binary complexes consisting of Ti and Zr in the range of 12-18 atomic% or 32-38 atomic%. 40. The sputtering target of claim 39, wherein the one or more alloying elements are selected from the group consisting of Ca, Mn, Fe, Co, Ni, Y and Hf. 40. The sputtering target of claim 39, wherein the one or more alloying elements comprise Y. 40. The sputtering target of claim 39, wherein the one or more alloying elements comprise Co. 40. The sputtering target of claim 39, wherein the one or more alloying elements comprise Ni. 40. The sputtering target of claim 39, wherein the one or more alloying elements have an atomic radius difference of at least 20% relative to Ti. 45. The method of claim 44, wherein the one or more alloying elements are from the group consisting of Be, B, C, P, S, Cs, Ba, La, Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er and Yb. A sputtering target, characterized in that selected. 45. The sputtering target of claim 44, wherein the one or more alloying elements are selected from the group consisting of Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er and Yb. 45. The sputtering target of claim 44, wherein the one or more alloying elements comprise Ba. 45. The sputtering target of claim 44, wherein the one or more alloying elements comprise La. 45. The sputtering target of claim 44, wherein the one or more alloying elements comprise Yb. Ti and one or more alloying elements having a melting temperature of at least about 2400 ° C .; Does not include binary alloys consisting of Ti and 35-50 atomic% W; And a sputtering target containing no binary alloy consisting of Ti and 6-8 atomic% Nb. 51. The sputtering target of claim 50, wherein the one or more alloying elements are selected from the group consisting of C, Mo and Ta. 51. The sputtering target of claim 50, wherein the one or more alloying elements comprise Mo. 51. The sputtering target of claim 50, wherein the one or more alloying elements comprise Ta. Ti and (1) a standard electrode potential of less than about -1.0 V; (2) a melting temperature of at least about 2400 ° C .; Or (3) an atomic radius difference of at least 8% relative to titanium; a sputtering target used to form a barrier layer for a silver-containing material comprising one or more alloying elements satisfying at least one of: 55. The sputtering target of claim 54, wherein the one or more alloying elements comprise Zr. Ti and (1) a standard electrode potential of less than about -1.0 V; (2) a melting temperature of at least about 2400 ° C .; Or (3) an atomic radius difference of at least 8% relative to titanium; and a sputtering target comprising one or more alloying elements that satisfy at least one of the following. 59. The sputtering target of claim 56, wherein the one or more alloying elements comprise Zr. Ti, Be, B, Al, Si, Ca, Sc, V, Cr, Mn, Fe, Sr, Y, Zr, Cs, Ba, La, Hf, Ta, Ce, Pr, Nd, Sm, Gd, Dy, Ho and Means for forming a Cu barrier layer by sputter-depositing a thin film from a target comprising one or more alloying elements selected from the group consisting of Er. 59. The method of claim 58, wherein the one or more alloying elements comprise Zr. 59. The method of claim 58, wherein the one or more alloying elements comprise V. 59. The method of claim 58, wherein the one or more alloying elements comprise Cr. 59. The method of claim 58, wherein the one or more alloying elements comprise Mn. 59. The method of claim 58, wherein the one or more alloying elements comprise Fe. 59. The method of claim 58, wherein the one or more alloying elements comprise Al. Forming a first layer on the substrate, the first layer comprising one or more alloying elements having an atomic radius difference of at least 8% relative to Ti and in an atmosphere free of nitrogen; And Forming a copper-containing layer on the first layer; And the first layer inhibits copper diffusion from the copper-containing layer to the substrate. 67. The method of claim 65, wherein said copper-containing layer is a layer based on copper. 67. The method of claim 65, wherein said one or more alloying elements are selected from the group consisting of Al, Ca, Mn, Fe, Co, Ni, Y, Zr, and Hf. 67. The method of claim 65, wherein said one or more alloying elements comprise Y. 66. The method of claim 65, wherein the one or more alloying elements have an atomic radius difference of at least 20% relative to Ti. 70. The group of claim 69, wherein the one or more alloying elements are Be, B, C, Si, P, S, Cs, Ba, La, Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er, and Yb A method for inhibiting copper diffusion to a substrate, characterized in that selected from. 70. The method of claim 69, wherein said one or more alloying elements comprise Ba. 70. The method of claim 69, wherein said one or more alloying elements comprise La. 70. The method of claim 69, wherein said one or more alloying elements comprise Yb. Forming a first layer on the substrate, the first layer comprising Ti and one or more alloying elements having a standard electrode potential of less than about -1.0 V in an atmosphere free of nitrogen; And Forming a copper-containing layer on the first layer; And the first layer inhibits copper diffusion from the copper-containing layer to the substrate. 75. The method of claim 74, wherein the one or more alloying elements are Be, B, Al, Si, Ca, Sc, V, Cr, Mn, Fe, Sr, Y, Zr, Cs, Ba, La, Hf, Ta, Ce, A method for inhibiting copper diffusion to a substrate, characterized in that it is selected from the group consisting of Pr, Nd, Sm, Gd, Dy, Ho and Er. 75. The method of claim 74, wherein said layer comprises said Ti and said one or more alloying elements. 75. The method of claim 74, wherein said layer is comprised of said Ti and said one or more alloying elements. 75. The method of claim 74, wherein said one or more alloying elements comprise Zr. 75. The method of claim 74, wherein the one or more alloying elements comprise V. 75. The method of claim 74, wherein said one or more alloying elements comprise Cr. 75. The method of claim 74, wherein the one or more alloying elements comprise Mn. 75. The method of claim 74, wherein said one or more alloying elements comprise Fe. 75. The method of claim 74, wherein said one or more alloying elements comprise Al. 75. The method of claim 74, wherein the first layer is formed by sputter deposition from a target comprising Ti and one or more alloying elements having a standard electrode potential of less than about -1.0V. How to suppress it. The copper diffusion from the copper-containing material formed by sputtering a sputtering target comprising Ti and one or more alloying elements not containing Al having a standard electrode potential of less than about -1.0 V in a nitrogen-free carbon atmosphere. Inhibiting Ti _x Q _y N _z thin film. Provided that "Q" represents one or more alloying elements. 86. The Ti _x Q _y N _z thin film of claim 85, wherein x = 0.1-0.7, y = 0.001-0.3 and z = 0.1-0.6. 86. The Ti _x Q _y N _z thin film of claim 85, wherein the thin film has a thickness of about 2-50 nm. 86. The Ti _x Q _y N _z thin film of claim 85, wherein the thin film has a thickness of about 2-20 nm. 86. The Ti _x Q _y N _z thin film according to claim 85, wherein the thin film further has an electrical resistivity of 300 µPa · cm or less. 86. The Ti _x Q _y N _z thin film of claim 85, wherein the thin film is used as a Cu barrier layer in a microelectronic device. 86. The method of claim 85, wherein the thin film has an average grain size of 100 nm or less, and the average grain size remains 100 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z thin film. 86. The method of claim 85, wherein the thin film has an average grain size of 10 nm or less, and the average grain size is maintained at 10 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z thin film. 86. The method of claim 85, wherein the thin film has an average grain size of 1 nm or less and the average grain size is maintained at 1 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z thin film. To suppress copper diffusion from a copper-containing material formed by sputtering a sputtering target comprising Ti and one or more alloying elements having a standard electrode potential of less than about -1.0 V in the presence of a nitrogen containing gas and an oxygen containing gas. Ti _x Q _y N _z O _w thin film. Provided that Q represents the one or more alloying elements. 95. The Ti _x Q _y N _z O _w thin film of claim 94, wherein x = 0.1-0.7, y = 0.001-0.3, z = 0.1-0.6 and w = 0.0001-0.0010. 95. The Ti _x Q _y N _z O _w thin film of claim 94, wherein the thin film has a thickness of about 2-50 nm. 95. The Ti _x Q _y N _z O _w thin film of claim 94, wherein the thin film has a thickness of about 2-20 nm. 95. The Ti _x Q _y N _z O _w thin film of claim 94, wherein the thin film has an electrical resistivity of 300 µPa · cm or less. 95. The method of claim 94, wherein the thin film has an average grain size of 100 nm or less, and the average grain size remains 100 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z O _w thin film. 95. The method of claim 94, wherein the thin film has an average grain size of 10 nm or less, wherein the average grain size is maintained at 10 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z O _w thin film. 95. The method of claim 94, wherein the thin film has an average grain size of 1 nm or less, and the average grain size is maintained at 1 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z O _w thin film. 95. The Ti _x Q _y N _z O _w thin film of claim 94, wherein the thin film is used as a Cu barrier layer in a microelectronic device. Ti _x Q _y N, which suppresses diffusion from copper-containing materials formed by sputtering a sputtering target comprising Ti and at least one alloying element having a melting temperature of at least about 2400 ° C. in a nitrogen-free nitrogen atmosphere. _z thin film. Provided that "Q" represents one or more alloying elements. 107. The Ti _x Q _y N _z thin film of claim 103, wherein x = 0.1-0.7, y = 0.001-0.3 and z = 0.1-0.6. 107. The Ti _x Q _y N _z thin film of claim 103, wherein the thin film has a thickness of about 2-50 nm. 107. The Ti _x Q _y N _z thin film of claim 103, wherein the thin film has a thickness of about 2-20 nm. 107. The Ti _x Q _y N _z thin film according to claim 103, wherein the thin film has an electrical resistivity of 300 µPa · cm or less. 107. The Ti _x Q _y N _z thin film of claim 103, wherein the thin film is used as a Cu barrier layer in microelectronic devices. 107. The method of claim 103, wherein the thin film has an average grain size of 100 nm or less, and the average grain size remains 100 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z thin film. 107. The method of claim 103, wherein the thin film has an average grain size of 10 nm or less, and the average grain size is maintained at 10 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z thin film. 107. The method of claim 103, wherein the thin film has an average grain size of 1 nm or less and the average grain size is maintained at 1 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z thin film. Ti _x which suppresses copper diffusion from a copper-containing material formed by sputtering a sputtering target comprising Ti and one or more alloying elements having a melting temperature of at least about 2400 ° C. in the presence of nitrogen-containing and oxygen-containing gases. Q _y N _z O _w thin film. Provided that "Q" represents one or more alloying elements. 118. The Ti _x Q _y N _z O _w thin film of claim 112, wherein x = 0.1-0.7, y = 0.001-0.3, z = 0.1-0.6 and w = 0.0001-0.0010. 118. The Ti _x Q _y N _z O _w thin film of claim 112, wherein the thin film has a thickness of about 2-50 nm. 118. The Ti _x Q _y N _z O _w thin film of claim 112, wherein the thin film has a thickness of about 2-20 nm. 118. The Ti _x Q _y N _z O _w thin film of claim 112, wherein the thin film has an electrical resistivity of 300 µPa · cm or less. 112. The method of claim 112, wherein the thin film has an average grain size of 100 nm or less, and the average grain size is maintained at 100 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z O _w thin film. 112. The method of claim 112, wherein the thin film has an average grain size of 10 nm or less, and the average grain size is maintained at 10 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z O _w thin film. 112. The method of claim 112, wherein the thin film has an average grain size of 1 nm or less, and the average grain size is maintained at 1 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z O _w thin film. 118. The Ti _x Q _y N _z O _w thin film of claim 112, wherein the thin film is used as a Cu barrier layer in microelectronic devices. Ti _x, which inhibits copper diffusion from a copper-containing material formed by sputtering a sputtering target comprising one or more alloying elements having an atomic radius difference of at least 8% compared to Ti and titanium in a nitrogen-free carbon atmosphere. Q _y N _z thin film. Provided that "Q" represents one or more alloying elements. 138. The Ti _x Q _y N _z thin film of claim 121, wherein x = 0.1-0.7, y = 0.001-0.3 and z = 0.1-0.6. 138. The Ti _x Q _y N _z thin film of claim 121, wherein the thin film has a thickness of about 2-50 nm. 138. The Ti _x Q _y N _z thin film of claim 121, wherein the thin film has a thickness of about 2-20 nm. 138. The Ti _x Q _y N _z thin film according to claim 121, wherein the thin film has an electrical resistivity of 300 µPa · cm or less. 138. The Ti _x Q _y N _z thin film of claim 121, wherein the thin film is used as a Cu barrier layer in microelectronic devices. 126. The method of claim 121, wherein the thin film has an average grain size of 100 nm or less, and the average grain size remains 100 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z thin film. 126. The method of claim 121, wherein the thin film has an average grain size of 10 nm or less, and the average grain size is maintained at 10 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z thin film. 126. The method of claim 121, wherein the thin film has an average grain size of 1 nm or less, and the average grain size is maintained at 1 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z thin film. Diffusion of copper from a copper-containing material formed by sputtering a sputtering target comprising one or more alloying elements having an atomic radius difference of at least 8% compared to Ti and titanium in the presence of nitrogen-containing and oxygen-containing gases Inhibiting Ti _x Q _y N _z O _w thin film. Provided that "Q" represents one or more alloying elements. 131. The Ti _x Q _y N _z O _w thin film of claim 130, wherein x = 0.1-0.7, y = 0.001-0.3, z = 0.1-0.6 and w = 0.0001-0.0010. 131. The Ti _x Q _y N _z O _w thin film of claim 130, wherein the thin film has a thickness of about 2-50 nm. 131. The Ti _x Q _y N _z O _w thin film of claim 130, wherein the thin film has a thickness of about 2-20 nm. 131. The Ti _x Q _y N _z O _w thin film of claim 130, wherein the thin film has an electrical resistivity of 300 µPa · cm or less. 131. The method of claim 130, wherein the thin film has an average grain size of 100 nm or less, and the average grain size is maintained at 100 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z O _w thin film. 133. The method of claim 130, wherein the thin film has an average grain size of 10 nm or less, and the average grain size is maintained at 10 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z O _w thin film. 131. The method of claim 130, wherein the thin film has an average grain size of 1 nm or less, and the average grain size is maintained at 1 nm or less even after exposure for at least about 30 minutes at a temperature of at least about 500 ° C during vacuum annealing. Ti _x Q _y N _z O _w thin film. 133. The Ti _x Q _y N _z O _w thin film of claim 130, wherein the thin film is used as a Cu barrier layer in a microelectronic device. Semiconductor substrates; A material supported by the semiconductor substrate, wherein the diffusion of metal into the inside is reduced; A material comprising said metal on said material; An intervening layer comprising Ti and one or more alloying elements; Wherein the intermediate layer is located between the material and the material to which diffusion of the metal into the interior is reduced, wherein the one or more alloying elements do not contain carbon or Al and (1) is less than about -1.0 V Standard electrode potential; (2) a melting temperature of at least about 2400 ° C .; Or (3) a difference in atomic radius of at least 8% relative to titanium; wherein the intermediate layer reduces diffusion from the material to the material relative to the amount of diffusion that occurs when no intermediate layer is present. Semiconductor structure. 139. The semiconductor structure of claim 139, wherein the metal to which diffusion is reduced is copper. 143. The method of claim 139, wherein the one or more alloying elements are Be, B, Si, Ca, Sc, V, Cr, Mn, Fe, Sr, Y, Zr, Cs, Ba, La, Hf, Ta, Ce, Pr, A semiconductor structure, characterized in that selected from the group consisting of Nd, Sm, Gd, Dy, Ho and Er. 139. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Zr. 139. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise V. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Cr. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Mn. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise B. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Nb. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Mo. 139. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Hf. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Ta. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise W. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Y. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Co. 139. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Ni. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Ba. 139. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise La. 143. The semiconductor structure of claim 139, wherein the one or more alloying elements comprise Yb. 139. The semiconductor structure of claim 139, wherein the metal for which diffusion is reduced is copper, and the material for reducing copper diffusion therein is an electrically insulating material. 139. The semiconductor structure according to claim 139, wherein the metal for which diffusion is reduced is copper, and the material for reducing copper diffusion therein comprises silicon dioxide. 139. The semiconductor structure of claim 139, wherein the metal for which diffusion is reduced is copper, and the material for reducing copper diffusion therein comprises BPSG. 139. The semiconductor structure of claim 139, wherein the metal for which diffusion is reduced is copper, and the material for reducing copper diffusion therein comprises silicon fluoride having a dielectric constant of 3.7 or less. 139. The semiconductor structure of claim 139, wherein the metal for which diffusion is reduced is copper and the material for reducing copper diffusion therein comprises an insulating material having a dielectric constant of 3 or less. A first layer comprising on the substrate Ti and at least one alloy element having an atomic radius difference of at least 8% compared to Ti selected from the group consisting of Ca, Mn, Fe, Co, Ni, Y, Zr and Hf Forming; And Forming a copper-containing layer on the first layer; And the first layer inhibits copper diffusion from the copper-containing layer to the substrate. At least as compared to Ti selected from the group consisting of Ti, Be, B, C, Si, P, S, Cs, Ba, La, Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er and Yb on the substrate. Forming a first layer comprising one or more alloying elements having an atomic radius difference of 20%; And Forming a copper-containing layer on the first layer; And the first layer inhibits copper diffusion from the copper-containing layer to the substrate. Ti, Be, B, Si, Ca, Sc, V, Cr, Mn, Fe, Sr, Y, Zr, Cs, Ba, La, Hf, Ta, Ce, Pr, Nd, Sm, Gd, Dy Forming a first layer comprising one or more alloying elements having a standard electrode potential of less than about −1.0 V selected from the group consisting of Ho and Er; And Forming a copper-containing layer on the first layer; And the first layer inhibits copper diffusion from the copper-containing layer to the substrate. About 2-inhibiting copper diffusion from a copper-containing material formed by sputtering a sputtering target comprising Ti and one or more alloying elements having a standard electrode potential of less than about -1.0 V in a nitrogen-free nitrogen atmosphere Ti _x Q _y N _z thin film with a thickness of 20 nm. Provided that "Q" represents one or more alloying elements. Semiconductor substrates; A material supported by the semiconductor substrate, the material of which diffusion of metal into the inside is reduced; A material comprising said metal on said material; An intervening layer comprising Ti and one or more alloying elements and having a thickness of about 2-20 nm; Wherein the intermediate layer is located between the material and the material to which diffusion of the metal into the material is reduced, wherein the one or more alloying elements comprise (1) a standard electrode potential of less than about −1.0 V; (2) a melting temperature of at least about 2400 ° C .; Or (3) a difference in atomic radius of at least 8% relative to titanium; wherein the interlayer reduces the diffusion of the metal from the material into the material relative to the amount of diffusion that occurs when no interlayer is present. The semiconductor structure which can be. 167. The semiconductor structure of claim 167, wherein the metal to which diffusion is reduced is copper. 167. The method of claim 167, wherein the one or more alloying elements are Be, B, Al, Si, Ca, Sc, V, Cr, Mn, Fe, Sr, Y, Zr, Cs, Ba, La, Hf, Ta, Ce, A semiconductor structure characterized in that it is selected from the group consisting of Pr, Nd, Sm, Gd, Dy, Ho and Er. Selected from the group consisting of Ti, Be, Ca, Sc, V, Mn, Fe, Sr, Zr, Cs, Ba, La, Hf, Ta, Ce, Pr, Nd, Sm, Gd, Dy, Ho and Er A sputtering target, comprising one or more alloying elements having a standard electrode potential of less than about -1.0 V, used to form a barrier layer for copper-containing materials. 172. The sputtering target of claim 170, wherein the copper-containing material is a material based on copper. 172. The sputtering target of claim 170, wherein the sputtering target comprises at least one alloying element that does not have a standard electrode potential of less than about -1.0V. 172. The sputtering target of claim 170, wherein the alloying elements in the sputtering target are elements having a standard electrode potential of less than about -1.0V. 172. The sputtering target of claim 170, wherein the sputtering target further comprises one or more alloying elements selected from the group consisting of B, Al, Si, Cr, and Y. Barriers to Cu-containing materials comprising Ti and one or more alloying elements having an atomic radius difference of at least 8% compared to titanium selected from the group consisting of Ca, Mn, Fe, Co, Ni, Zr and Hf Sputtering targets used to form layers. 175. The sputtering target of claim 175, wherein the sputtering target further comprises one or more of Al and Y. Selected from the group consisting of Ti and Al and Be, Ca, Sc, V, Mn, Fe, Sr, Cs, Ba, La, Hf, Ta, Ce, Pr, Nd, Sm, Gd, Dy, Ho and Er A sputtering target comprising one or more alloying elements having a standard electrode potential of less than about -1.0V. 181. The sputtering target of claim 177, wherein the sputtering target further comprises one or more alloying elements having a standard electrode potential of less than about -1.0 V selected from the group consisting of B, Cr, and Y. One or more alloying elements having a Ti and a standard electrode potential of less than about −1.0 V; Does not include TiAl alloys or TiSi binary alloys; And a sputtering composition further comprising no TiZr binary alloy in which Zr in the range of 12-18 atomic% or 32-38 atomic% is present. 179. The method of claim 179, wherein the one or more alloying elements are Be, B, Ca, Sc, V, Cr, Mn, Fe, Sr, Y, Cs, Ba, La, Hf, Ta, Ce, Pr, Nd, Sm, A sputtering composition, characterized in that it is selected from the group consisting of Gd, Dy, Ho and Er. Ti and one or more alloying elements having an atomic radius difference of at least 8% relative to titanium; Does not contain binary complexes of alloying elements selected from the group consisting of Ti, Al and Si; And a sputtering composition further comprising a binary composite composed of Ti and Zr in which Zr in a range of 12-18 atomic% or 32-38 atomic% exists. 181. The method of claim 181, wherein the one or more alloying elements are selected from the group consisting of Ca, Mn, Fe, Co, Ni, Y, Hf, Be, B, C, P, S, Cs, Ba, La, Ce, Pr, Nd, Sm, A sputtering composition, characterized in that it is selected from the group consisting of Gd, Dy, Ho, Er and Yb. Ti and (1) a standard electrode potential of less than about −1.0 V; (2) a melting temperature of at least about 2400 ° C .; Or (3) an atomic radius difference of at least 8% relative to titanium; and a sputtering composition comprising one or more alloying elements that satisfy at least one of the above, wherein the sputtering composition is used to form a barrier layer for silver-containing materials. Ti and (1) a standard electrode potential of less than about −1.0 V; (2) a melting temperature of at least about 2400 ° C .; Or (3) an atomic radius difference of at least 8% relative to titanium; and a sputtering composition comprising one or more alloying elements satisfying at least one of the following: used to form a barrier layer for an aluminum-containing material.