Wiring Board

Abstract

To provide a wiring board having wiring formed on a substrate, a method for manufacturing the wiring board, and a semiconductor device including the wiring board.SOLUTION: A wiring board 100 includes a substrate 102 including a first element, a diffusion layer 106 in contact with the substrate 102 and containing a first metal element, and a first metal film 104 in contact with the diffusion layer 106 and containing a second metal element. The diffusion layer 106 has a region containing at least a first element and a first metal element, and a region containing the first metal element and a second metal element. The concentration of the second metal element in the diffusion layer 106 may decrease as it approaches the substrate 102 in the thickness direction. The concentration of the first element in the diffusion layer 106 may decrease as it approaches the first metal film 104 in the thickness direction.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a wiring board having wiring formed on a substrate, a method for manufacturing a wiring board, and a semiconductor device including the wiring board. [Background technology]

[0002] Electronic devices usually use a basic structure including a substrate and wiring provided thereon (hereinafter, referred to as a wiring substrate). Such wiring substrates not only function as semiconductor devices themselves, but are also widely used as substrates for electrically connecting various electronic components, or as substrates (interposers) for mounting semiconductor devices on electronic devices. Various methods for providing wiring on a substrate have been developed. For example, the methods disclosed in Patent Documents 1 and 2 provide a film containing a metal oxide between an insulating substrate and wiring, thereby improving adhesion between the substrate and wiring. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Specification of Patent Publication No. 2016 / 533430 [Patent Document 2] Specification of Patent Publication No. 2016 / 533429 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a wiring board and a manufacturing method thereof. For example, an object of the present disclosure is to provide a wiring board having high adhesion between a substrate and wiring and a manufacturing method thereof. Alternatively, an object of the present disclosure is to provide a semiconductor device having this wiring board. [Means for solving the problem]

[0005] One embodiment of the present disclosure is a wiring board. The wiring board has a substrate including a first element, a diffusion layer including the first metal element and in contact with the substrate, and a first metal film including a second metal element and in contact with the diffusion layer. The diffusion layer has a region including at least the first element and the first metal element, and a region including the first metal element and the second metal element.

[0006] One embodiment of the present disclosure is a method for manufacturing a wiring substrate, which includes forming a first intermediate layer including an oxide of a first metal element on a substrate including the first element, converting the first intermediate layer into a second intermediate layer by diffusing the first element into the first intermediate layer, forming a first metal film including a second metal element on the second intermediate layer, and converting the second intermediate layer into a diffusion layer by diffusing the second metal element into the second intermediate layer. [Brief description of the drawings]

[0007] [Figure 1] 1A and 1B are a schematic cross-sectional view of a wiring board according to an embodiment, and a schematic diagram of a concentration profile in the thickness direction of the wiring board. [Diagram 2] 4 is a schematic diagram of an element concentration profile in a thickness direction of a wiring board according to an embodiment. [Diagram 3] 4 is a schematic diagram of an element concentration profile in a thickness direction of a wiring board according to an embodiment. [Figure 4] 4 is a schematic diagram of an element concentration profile in a thickness direction of a wiring board according to an embodiment. [Diagram 5] 4 is a schematic diagram of an element concentration profile in a thickness direction of a wiring board according to an embodiment. [Figure 6] FIG. 1 is a schematic cross-sectional view of a wiring board according to an embodiment. [Figure 7] 1A to 1C are schematic cross-sectional views showing a method for manufacturing a wiring board according to an embodiment. [Figure 8] 1A to 1C are schematic cross-sectional views showing a method for manufacturing a wiring board according to an embodiment. [Figure 9] 1A to 1C are schematic cross-sectional views showing a method for manufacturing a wiring board according to an embodiment. [Figure 10] 1A to 1C are schematic cross-sectional views showing a method for manufacturing a wiring board according to an embodiment. [Figure 11] 1 is a schematic cross-sectional view of a semiconductor device including a wiring board according to an embodiment. [Figure 12] 1 is a schematic cross-sectional view of a semiconductor device including a wiring board according to an embodiment. [Figure 13] 1 is a schematic cross-sectional view of a semiconductor device including a wiring board according to an embodiment. [Figure 14] 1 shows the results of energy dispersive X-ray analysis of a wiring board according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, each embodiment of the present disclosure will be described with reference to the drawings, etc. However, the present disclosure can be implemented in various forms without departing from the spirit of the present disclosure, and should not be interpreted as being limited to the description of the embodiments exemplified below.

[0009] In order to clarify the description, the drawings may show the width, thickness, shape, etc. of each part in a schematic manner compared to the actual embodiment, but these are merely examples and do not limit the interpretation of the present disclosure. In this specification and each drawing, elements having the same functions as those described in the previous drawings may be given the same reference numerals, and duplicated descriptions may be omitted.

[0010] In this specification and the claims, when describing an aspect in which another structure is placed above or below a certain structure, the term "above" or "below" is used, unless otherwise specified, to include both a case in which another structure is placed directly above or below a certain structure so as to be in contact with the certain structure, and a case in which another structure is placed above or below a certain structure with another structure in between.

[0011] In this specification and claims, the expression "a structure is exposed from another structure" means an aspect in which a part of a structure is not covered by another structure, and also includes an aspect in which the part not covered by the other structure is covered by yet another structure.

[0012] (First embodiment) In this embodiment, a wiring board 100 according to one embodiment of the present disclosure will be described.

[0013] 1.Basic structure 1(A) shows a schematic cross-sectional view of a wiring board 100. The wiring board 100 includes a substrate 102, a diffusion layer 106 located on the substrate 102 and in contact with the substrate 102, and a first metal film 104 located on the diffusion layer 106 and in contact with the diffusion layer 106. The wiring board 100 may further include a second metal film 108 located on the first metal film 104 and in contact with the first metal film 104 as an optional configuration.

[0014] The substrate 102 includes a first element. Here, the first element is selected from elements other than oxygen and is an element included in the main component of the substrate 102. In this specification and claims, the main component of a certain composition is a component that occupies 90% by weight or more of the composition. Examples of the substrate 102 include a glass substrate, a quartz substrate, a semiconductor substrate including a semiconductor such as silicon, germanium, gallium arsenide, or gallium nitride, a ceramic substrate including a ceramic such as alumina or zirconia, and a substrate including a single crystal metal oxide such as a sapphire substrate. In the case of a substrate mainly composed of glass, a resin may be compounded. When the above-mentioned substrate is used, the first element is selected from silicon, germanium, aluminum, zirconium, arsenic, nitrogen, and the like.

[0015] Among the above-mentioned substrates, a glass substrate is inexpensive and has excellent insulating properties, and is therefore preferable when the wiring substrate 100 is used as an interposer for a semiconductor device. Examples of glass contained in the glass substrate include soda-lime glass, fluoride glass, phosphate glass, and borate glass.

[0016] The surface roughness of the substrate 102 is not limited, and may be, for example, 0.1 nm or more, 1 nm or more, or 5 nm or more. The surface roughness of the substrate 102 may be 200 nm or less, 100 nm or less, or 50 nm or less. The surface roughness of the substrate 102 may be 0.1 nm or more and 200 nm or less, 1 nm or more and 100 nm or less, or 5 nm or more and 50 nm or less. The surface roughness may be measured, for example, using an optical interference microscope. When a wiring having a relatively small thickness is provided on the substrate 102, the surface roughness of the substrate 102 is reflected on the surface of the wiring, but by adjusting the surface roughness of the substrate 102 to the above-mentioned range, the increase in the surface roughness of the wiring is also suppressed. Therefore, when the wiring substrate 100 is applied to a high-frequency circuit board, the transmission loss can be reduced. Furthermore, when the wiring is processed by photolithography, scattering of light from an exposure machine can be suppressed, and the fine processing of the wiring can be prevented from being hindered.

[0017] Here, the surface roughness can be evaluated by the arithmetic mean roughness Ra, which is a parameter expressed by the following formula: In this formula, L is the measurement length on the substrate 102 to be evaluated, and f(x) is the height when the direction of the measurement length is x. Ra is the absolute value of the height over the measurement length, averaged over the measurement length.

number

[0018] An example of a method for measuring the arithmetic mean roughness Ra is as follows. First, a plurality of arbitrary measurement regions are selected on the substrate 102. The size of the measurement region may be, for example, a rectangle of 0.30 mm×0.22 mm. For example, the four corners and five points in the center of the substrate 102 may be selected as the measurement regions. Next, two arbitrary points are set in each of the plurality of regions. The distance between these two points is set to 0.1 mm, which corresponds to the measurement length L. The arithmetic mean roughness Ra between these two points is measured, and the average of the arithmetic mean roughness Ra obtained in the plurality of measurement regions is adopted as the surface roughness of the substrate 102. For example, when the four corners and five points in the center of the substrate 102 are selected as the measurement regions, the average of the five measurement results becomes the surface roughness of the substrate 102. Note that a plurality of measurements may be performed in each measurement region, and the average may be adopted as the arithmetic mean roughness Ra in one measurement region. The arithmetic mean roughness Ra can be measured, for example, by using a 3D optical profiler using a white light interferometer (for example, 3D optical profiler Zygo New View5000 manufactured by Zygo Corporation).

[0019] The first metal film 104 contains a zero-valent metal element (second metal element) and can function as a wiring of the wiring board 100, or as a seed layer for forming the second metal film 108 or various wirings (not shown) provided on the wiring board 100 by electrolytic plating. Examples of the second metal element include copper, titanium, chromium, nickel, and gold. There is no restriction on the thickness of the first metal film 104, and it can be, for example, 0.5 μm or more, 1 μm or more, or 5 μm or more, and 50 μm or less, 30 μm or less, or 20 μm or less. The thickness of the first metal film 104 may be 0.5 μm or more and 50 μm or less, 1 μm or more and 30 μm or less, or 5 μm or more and 20 μm or less. By setting the thickness of the first metal film 104 within this range, it is possible to ensure sufficient conductivity as a wiring. Furthermore, for example, even when the first metal film 104 is formed by a plating method, it can be formed in a short time, and even when the first metal film 104 is formed by photolithography, fine processing can be easily performed.

[0020] The diffusion layer 106 has a function of firmly adhering the first metal film 104 to the substrate 102, and is therefore also called an adhesion layer. The diffusion layer 106 is generated by mutual diffusion of an intermediate layer provided between the first metal film 104 and the substrate 102. The intermediate layer contains a first metal element. For example, the intermediate layer contains an oxide or nitride of a first metal, and examples of the first metal include zinc, titanium, zirconium, aluminum, and tin. The region of the intermediate layer containing the first metal is the diffusion layer 106. The thickness of the diffusion layer 106 may be 1 nm or more. This allows the diffusion layer 106 to follow the surface roughness of the substrate 102, and not only can high adhesion between the first metal film 104 and the substrate 102 be ensured, but also microfabrication can be performed simultaneously with the first metal film 104. The thickness of the diffusion layer 106 may be 1 μm or less, 100 nm or less, 20 nm or less, or 10 nm or less. The thickness of the diffusion layer 106 may be 1 nm or more and 1 μm or less, 1 nm or more and 100 nm or less, 1 nm or more and 20 nm or less, or 1 nm or more and 10 nm or less. This allows the diffusion layer 106 to be formed in a short time, and ensures that no etching residue remains on the substrate 102 during processing such as etching, thereby ensuring insulation between adjacent wirings. For example, when the arithmetic mean roughness Ra of the substrate 102 is 5 nm, the thickness of the diffusion layer 106 may be set in the range of 10 nm or more and 20 nm or less.

[0021] 2. Composition of the diffusion layer In addition to the first metal element, the diffusion layer 106 further includes the first element contained in the substrate 102 and the second metal element contained in the first metal film 104. More specifically, the diffusion layer 106 includes at least one of a region where the first element, the first metal element, and the second metal element coexist, a region where the first metal element and the first element coexist, and a region where the first metal element and the second metal element coexist. For example, the diffusion layer 106 may have a region including the first metal element and the first element, and a region including the first metal element and the second metal element.

[0022] Therefore, the thickness of the diffusion layer 106 does not necessarily coincide with the thickness of the intermediate layer, and can be defined as the thickness of a portion where at least one of the above three regions exists. In this case, the thickness can be measured by energy dispersive X-ray (EDX) analysis. Specifically, a sample in which at least the diffusion layer 106 and the first metal film 104 are arranged on the substrate 102 is processed using a focused ion beam (FIB) to expose a cross section, and an electron beam is irradiated from the substrate 102 side so as to scan the interface between each layer, and characteristic X-rays are detected using a Si drift detector or the like. The atomic composition ratio (atomic %) of each element is obtained based on the intensity of the characteristic X-ray. This allows the element distribution in the depth direction to be obtained, and the above regions to be specified. The thickness of the portion where at least one of these regions exists can be calculated to determine the thickness of the diffusion layer 106.

[0023] Fig. 1(B) shows a schematic of the concentration profiles of the first element, the first metal element, and the second metal element in the thickness direction of the wiring substrate 100. In Fig. 1(B) to Fig. 5(B) below, the vertical axis is the normalized element concentration (i.e., the number of atoms of the first element, the first metal element, and the second metal element per unit volume), and the horizontal axis is the depth of the wiring substrate 100. The depth is the distance from the top surface of the first metal film 104 in the direction toward the substrate 102 along the normal to the top surface of the first metal film 104.

[0024] As shown in FIG. 1B, the concentration 102a of the first element decreases from the interface 103 between the substrate 102 and the diffusion layer 106 toward the first metal film 104 in the thickness direction. Similarly, the concentration 104a of the second metal element decreases from the interface 105 between the diffusion layer 106 and the first metal film 104 toward the substrate 102 in the thickness direction. These concentration changes may be continuous. Here, the interface 103 is a surface located between a region where the first metal element does not exist or is substantially undetectable and a region where the first metal element exists or is detectable, and is closer to the substrate 102 than the first metal film 104. The interface 105 is a surface located between a region where the first metal element does not exist or is substantially undetectable and a region where the first metal element exists or is detectable, and is closer to the first metal film 104 than the substrate 102 (see FIG. 1B). Between these interfaces 103, 105 is a diffusion layer 106, and in the diffusion layer 106, a plot of the concentration 106a of the first metal element against the depth gives at least one peak (FIG. 1(B)).

[0025] Therefore, in the diffusion layer 106, the plot of the concentration 104a of the second metal element versus depth in the wiring substrate 100 (the dashed line in FIG. 1B) intersects with the plot of the first element versus depth (the dashed line in FIG. 1B). The concentration 102a of the first element, the concentration 106a of the first metal element, and the concentration 104a of the second metal element can be measured by, for example, EDX analysis.

[0026] 1(B), the concentration 104a of the second metal element decreases toward the substrate 102 in the diffusion layer 106, and becomes substantially undetectable at the interface 103. Similarly, the concentration 102a of the first element decreases toward the first metal film 104 in the diffusion layer 106, and becomes substantially undetectable at the interface 105. In other words, the first element, the first metal element, and the second metal element coexist throughout the diffusion layer 106.

[0027] The concentration profiles of the first element and the second metal element in the diffusion layer 106 are not limited to those shown in Fig. 1(B). For example, as shown in Fig. 2(A), the diffusion layer 106 may have a region 106b on the interface 105 side where the first element is not present or is substantially undetectable. Alternatively, as shown in Fig. 2(B), the diffusion layer 106 may have a region 106c on the interface 103 side where the second metal element is not present or is substantially undetectable.

[0028] Alternatively, as shown in FIG. 3(A), the second metal element may be contained not only in the diffusion layer 106 but also in the substrate 102. In this case, the concentration 104a of the second metal element in the substrate 102 decreases with increasing distance from the interface 103. Conversely, the first element may be contained not only in the diffusion layer 106 but also in the first metal film 104 (FIG. 3(B)). In this case, the concentration 102a of the first element in the first metal film 104 decreases with increasing distance from the interface 105.

[0029] The diffusion layer 106 may be configured to combine the above-mentioned concentration profiles. For example, as shown in Fig. 4(A), the diffusion layer 106 may have both the region 106b and the region 106c on the interface 105 side and the interface 103 side, respectively. In this case, the region in the diffusion layer 106 where the first element, the first metal element, and the second metal element coexist is sandwiched between the regions 106b and 106c.

[0030] 4(B), the diffusion layer 106 may have a region 106c, and the first element may be contained not only in the diffusion layer 106 but also in the first metal film 104. Conversely, as shown in FIG 5(A), the diffusion layer 106 may have a region 106b, and the second metal element may be contained not only in the diffusion layer 106 but also in the substrate 102. Alternatively, as shown in FIG 5(B), the first element may be contained not only in the diffusion layer 106 but also in the first metal film 104, and the second metal element may be contained not only in the diffusion layer 106 but also in the substrate 102.

[0031] In either concentration profile, the plot of the concentration 104a of the second metallic element versus depth in the wiring substrate 100 intersects with the plot of the concentration of the first element versus depth in the diffusion layer 106. Thus, in addition to the first metallic element, at least one of the first element and the second metallic element is contained in any region of the diffusion layer 106, and there is no region that contains the first metallic element but not both the first element and the second metallic element.

[0032] 3. Variations As shown in FIG. 6(A), the substrate 102 of the wiring substrate 100 may have a through hole 110. In this case, the diffusion layer 106 and the first metal film 104 are provided so as to cover the upper and lower surfaces of the substrate 102 and the side walls of the through hole 110. The second metal film 108, which is provided as an optional configuration, may also be arranged so as to cover the upper and lower surfaces of the substrate 102 and the side walls of the through hole 110. If the entire through hole 110 is not blocked by the first metal film 104 or the second metal film 108, a filler 112 may be formed so as to fill the through hole 110. Examples of the filler 112 include organic compounds such as epoxy resin, acrylic resin, polyimide, polyamide, and polyester. The organic compound may be mixed with an inorganic material such as silicon oxide. Alternatively, as shown in FIG. 6(B), the second metal film 108 or the first metal film 104 may be provided so as to block the through hole 110. As described below, the first metal film 104, or the stack of the first metal film 104 and the second metal film 108, can function as a through-wiring for electrically connecting various elements and semiconductor devices mounted on the substrate 102.

[0033] In the wiring board 100 having the above-mentioned configuration, as experimentally proven in the examples, a large adhesive force is obtained between the substrate 102 and the first metal film 104 due to the presence of the diffusion layer 106. In addition, since the diffusion layer 106 does not substantially have a region in which the oxide of the first element exists alone, the diffusion layer 106 has a high etching resistance compared to a film having a region consisting essentially of only the oxide of the first element. Therefore, the diffusion layer 106 exhibits an etching rate similar to that of the first metal film 104, and when the first metal film 104 is etched, etching (side etching) of the diffusion layer 106 located under the first metal film 104 is unlikely to occur. In particular, when the diffusion layer 106 has a region in which the first element, the first metal element, and the second metal element coexist, such side etching is prevented because the intermediate layer does not exist alone, and a high adhesive force can be expressed. As a result, the phenomenon in which the first metal film 104 peels off from the substrate 102 can be effectively suppressed, and a highly reliable wiring board and a semiconductor device including the same can be provided.

[0034] Second embodiment In this embodiment, a method for manufacturing the wiring board 100 described in the first embodiment will be described. Descriptions of configurations that are the same as or similar to the configuration described in the first embodiment may be omitted.

[0035] First, the first intermediate layer 120, which is a precursor of the diffusion layer 106, is formed on the substrate 102-1 (FIG. 7, S1). The first intermediate layer 120 contains an oxide of a first element and is formed by a sputtering method, a physical vapor deposition (PVP) method such as electron beam deposition or vacuum deposition, or a sol-gel method. When using the sol-gel method, a metal alkoxide such as tetraethyl zinc, tetraethoxy titanium, or tetraethoxy zirconium is used as a raw material, and a solution or a mixed liquid containing this is applied to the substrate 102-1 by a spin coating method, a dip coating method, a printing method, or the like, and then the metal alkoxide is hydrolyzed to form the first intermediate layer 120. The thickness of the first intermediate layer 120 may be 5 nm or more, 20 nm or less, or 15 nm or less. The thickness of the first intermediate layer 120 may be 5 nm or more and 20 nm or less, or 5 nm or more and 15 nm or less.

[0036] The thickness of the intermediate layer can be measured by a thin film calibration curve method. Specifically, a metal thin film having a known thickness and containing the metal contained in the intermediate layer 120 is used as a standard sample, and the fluorescent X-ray intensity obtained by irradiating the metal thin film with X-rays is measured. A calibration curve showing the relationship between thickness and fluorescent X-ray intensity is prepared using a plurality of samples with different thicknesses. Next, a similar measurement is performed on the intermediate layer 120 formed on the substrate 102, and the thickness is estimated from the obtained fluorescent X-ray intensity using the calibration curve. In this measurement, measurements are performed in a plurality of regions of the intermediate layer 120, and the thickness obtained in each region is averaged, and the obtained value can be used as the thickness of the intermediate layer 120. For example, five regions at the four corners and center of the substrate 102 can be selected as the plurality of regions.

[0037] An example of the measuring device is a Seiko Instruments SFT9450 fluorescent X-ray analyzer equipped with both a semiconductor detector and a proportional counter as detectors and a collimator with a diameter of 0.1 mm. Using this device, the thickness of the intermediate layer 120 is measured according to the above-mentioned method under conditions of a tube current of 1500 μA and a measurement time of 30 seconds.

[0038] Thereafter, the substrate 102-1 and the first intermediate layer 120 formed thereon are subjected to a heat treatment, so that the first element contained in the substrate 102-1 is diffused into the first intermediate layer 120. The heat treatment may be performed at a temperature set within a temperature range of, for example, 100° C. or more, 200° C. or more, 250° C. or more, or 350° C. or more, and 700° C. or less, 600° C. or less, or 550° C. or less. This temperature range may be 100° C. or more and 700° C. or less, 200° C. or more and 700° C. or less, 250° C. or more and 600° C. or less, or 350° C. or more and 550° C. or less. Depending on the heating temperature, the heating time may be, for example, 10 minutes or more, 15 minutes or more, or 30 minutes or more, and may be 5 hours or less, or 2 hours or less. A typical heating time is 1 hour. The heating time may be 10 minutes or more and 5 hours or less, 15 minutes or more and 5 hours or less, or 30 minutes or more and 2 hours or less. When heating at a temperature higher than the heat resistance temperature (glass transition temperature or melting point) of the substrate 102, it is preferable to perform the heat treatment for a short time of about 1 to 30 seconds. This heat treatment converts the first intermediate layer 120 into a second intermediate layer 122 containing the first metal element and the first element (FIG. 7, S2). At least a part of the first metal element exists as an oxide. The substrate 102-1 and the first intermediate layer 120 are converted into the substrate 102-2 and the second intermediate layer 122, respectively, by mutual diffusion.

[0039] Subsequently, the metal film 104-1 is formed on the second intermediate layer 122. The second intermediate layer 122 may be formed by, for example, electroless plating, sputtering, chemical vapor deposition (CVD) including metalorganic chemical vapor deposition (MOCVD), or PVD such as vacuum deposition or electron beam deposition. The temperature at this time may be room temperature (20° C. or more and 25° C. or less), or a temperature above room temperature and below 100° C. or below 50° C. (FIG. 7, S3). The temperature at the time of forming the metal film 104-1 may be above room temperature and below 100° C., or above room temperature and below 50° C.

[0040] After this, a heat treatment is performed again to diffuse the first metal contained in the metal film 104-1 into the second intermediate layer 122. The temperature and time of the heat treatment can be appropriately selected from the above-mentioned ranges. At this time, the first element contained in the substrate 102 may further diffuse into the second intermediate layer 122. By this heat treatment, the second intermediate layer 122 is converted into the diffusion layer 106 having the concentration profile described in the first embodiment (FIG. 7, S4). In addition, the metal film 104-1 after mutual diffusion with the second intermediate layer 122 is defined as the first metal film 104. Although not shown, a second metal film 108 may be formed on the first metal film 104. The second metal film 108 can be formed by a sputtering method, a CVD method, a PVD method, or the like. Alternatively, the first metal film 104 may be used as a seed layer, and the second metal film 108 may be formed by supplying power to the first metal film 104.

[0041] When manufacturing a wiring board 100 having through holes 110, first, through holes 110 are provided in a substrate 102 (FIG. 8, S10). Through holes 110 may be formed by etching such as plasma etching or wet etching, laser irradiation, or mechanical processing such as sandblasting or ultrasonic drilling. If necessary, after forming through holes 110, substrate 102 may be treated with hydrofluoric acid to flatten the upper and lower surfaces of substrate 102 and the side walls of through holes 110.

[0042] After the through-hole 110 is formed, the first intermediate layer 120 is formed so as to cover the upper and lower surfaces of the substrate 102 and the side walls of the through-hole 110 (FIG. 8, S11). Then, the first intermediate layer 120 is converted into the second intermediate layer 122 by the above-mentioned heat treatment (FIG. 8, S12), and the metal film 104-1 is formed on the second intermediate layer 122 (FIG. 8, S13). Then, the above-mentioned heat treatment is performed to convert the second intermediate layer 122 into the diffusion layer 106 (FIG. 9, S14).

[0043] Thereafter, the second metal film 108 is formed on a part of the upper and lower surfaces of the substrate 102. For example, as shown in S15 of Fig. 9, a resist mask 124 is provided on the first metal film 104 so as to cover the area where the second metal film 108 is not provided. The resist mask 124 may be formed by applying and hardening a liquid resist, but since the substrate 102 has the through-holes 110, the resist mask 124 can be efficiently formed by attaching a film-like resist to the upper and lower surfaces of the substrate 102 and then performing exposure and development.

[0044] Thereafter, the first metal film 104 is supplied with electricity to perform electrolytic plating. As a result, the second metal film 108 is formed on the first metal film 104 exposed from the resist mask 124 (FIG. 9, S16). Thereafter, the resist mask 124 is removed (FIG. 10, S17), and the first metal film 104 and the diffusion layer 106 exposed from the second metal film 108 are removed by etching (FIG. 10, S18). The etching can be performed using an etchant containing an acid such as sulfuric acid. By the above process, the wiring board 100 having the through hole 110 can be manufactured. Although a detailed description is omitted, the through hole 110 may be formed after the first metal film 104 is formed or after the second metal film 108 is formed.

[0045] As described above, the diffusion layer 106 of the present disclosure exhibits an etching rate similar to that of the first metal film 104, so that side etching of the diffusion layer 106 does not occur or occurs very slowly even in the etching process (S18) of the first metal film 104. Therefore, a sufficient contact area can be provided between the first metal film 104 and the substrate 102 via the diffusion layer 106. As a result, peeling of the first metal film 104 and the second metal film 108 can be effectively prevented.

[0046] Third embodiment In this embodiment, a semiconductor device using the wiring substrate 100 described in the first and second embodiments will be described. Here, a semiconductor device using the wiring substrate 100 obtained in step S18 of FIG. 10 will be described as a representative example.

[0047] The semiconductor device 130 shown in FIG. 11 has a main substrate 132 and a plurality of wiring substrates 100 (wiring substrates 100-1, 100-2, 100-3) stacked thereon. There is no limit to the number of wiring substrates 100, and it is determined according to the performance required for the semiconductor device 130. Various semiconductor chips (memory devices, central processing units) and semiconductor elements (microelectromechanical systems (MEMS), etc.) are connected to the main substrate 132. FIG. 11 shows an example in which a central processing unit 133 is installed on the main substrate 132. As described in the first embodiment, the wiring substrate 100 functions as a through-wiring, and has a second metal film 108 and a first metal film 104 (hereinafter, these are collectively referred to as a connection wiring 134) provided on the upper and lower surfaces of the substrate 102, and the connection wiring 134 contributes to electrical connection in the vertical direction in the semiconductor device 130. The connection wiring 134 of the wiring board 100-1 in the bottom layer is electrically connected to the terminal 138 provided on the main board 132 through the bump 136-1 via a via hole or wiring arranged between the interlayer insulating layers 142, 142. The connection wiring 134 provided on the upper part of the wiring board 100-1 is electrically connected to the wiring board 100-2 through the bump 136-2 via a via hole or wiring installed between the interlayer insulating layers 139, 140. Similarly, the wiring board 100-2 and the wiring board 100-3 are also electrically connected to each other through the bump 136-3. The bump 136 includes a metal such as indium, copper, or gold, or an alloy such as solder.

[0048] As in semiconductor device 150 shown in Fig. 12, stacked wiring boards 100 may be different in size or shape, and the number of wiring boards 100 stacked on main substrate 132 may also be different. In the example shown in Fig. 12, two wiring boards 100-4 and 100-5 are stacked in some regions, and three wiring boards 100-1, 100-2, and 100-3 are stacked in other regions.

[0049] The semiconductor device 160 shown in FIG. 13 has a structure in which a plurality of semiconductor chips 162-1 and 162-2 are stacked on the main substrate 132 via the wiring substrate 100. Terminals 164 and 166 are formed on the semiconductor chips 162-1 and 162-2, respectively, and these are electrically connected to the connection wiring 134 of the wiring substrate 100-1 via bumps 168. Examples of the semiconductor chips include the semiconductor chip 162-1 as a drive chip and the semiconductor chip 162-2 as a memory chip. This electrically connects the semiconductor chips 162-1 and 162-2 to each other. The semiconductor chip 162-2 and the main substrate 132 may also be electrically connected by a wire wiring 170. Although the connection wiring 134 is shown to be directly connected to the bumps 136 and 168 in FIG. 11 to FIG. 13, other wiring such as lead wiring may be provided between the bumps 136 and 168 and the connection wiring 134. EXAMPLES

[0050] 1. Example 1 In this example, the results of analyzing elements contained in wiring board 100 manufactured according to the manufacturing method described in the second embodiment will be described.

[0051] The structure of the wiring board 100 is as shown in FIG. 1(A), and the specific manufacturing method is as follows. A film containing zinc oxide was formed on a glass substrate (30 cm×40 cm, thickness 0.5 mm, surface roughness 5 nm) by a sol-gel method to form a first intermediate layer 120 (thickness 15 nm). After that, the first intermediate layer 120 was converted into a second intermediate layer 122 by heating at 550° C. for 1 hour. Subsequently, a copper film (thickness 0.5 μm) was formed on the second intermediate layer 122 as the first metal film 104 by applying an electroless plating method. After that, the second intermediate layer 122 was converted into a diffusion layer 106 by heating again at 450° C. for 1 hour.

[0052] As comparative examples, samples were also prepared using three substrates with surface roughnesses of 5 nm, 200 nm, and 1 μm (1000 nm), in which the first metal film 104 was formed directly on the substrate without forming the first intermediate layer 120. These samples correspond to samples 8 to 10 in Table 1, which will be described later, and do not have the diffusion layer 106.

[0053] The elemental analysis was performed by processing the wiring substrate 100 after heating using FIB to expose the cross section, and scanning the interface between each layer from the substrate 102 side using EDX. The obtained characteristic X-ray intensity was converted into atomic composition ratio, and the element distribution in the depth direction was evaluated. As a measuring device, a transmission electron microscope (manufactured by Hitachi High-Technologies, model number: HD-2700) equipped with an elemental analyzer was used, and an electron beam with a beam diameter of about 0.2 nm at an acceleration voltage of 200 kV was irradiated onto the wiring substrate 100, and the generated characteristic X-ray was detected using a Si drift detector. As an elemental analyzer, EMAX Evolution manufactured by Horiba, Ltd. was used. The energy resolution was about 130 eV, the X-ray take-off angle was 24.8°, and the solid angle was 2.2 sr. The number of acquisition points was 100, and each acquisition time was 1 second.

[0054] The EDX analysis results are shown in FIG. 14. FIG. 14 shows the change in concentration of zinc, silicon, and copper with respect to the depth of the wiring substrate 100. As shown in FIG. 14, zinc is substantially undetectable in the region from 0 nm to 35 nm deep and in the region deeper than 50 nm deep. It can therefore be seen that the interface 103 between the substrate 102 and the diffusion layer 106, and the interface 105 between the diffusion layer 106 and the first metal film 104 are located at depths of 35 nm and 50 nm, respectively. It was confirmed that the plot of the concentration of zinc contained in the diffusion layer 106 shows one peak in the diffusion layer 106.

[0055] From FIG. 14, it can be seen that the concentration of silicon, which is the first element contained in the substrate 102, decreases as it approaches the first metal film 104 from the interface 103. Similarly, it can be seen that the concentration of copper contained in the first metal film 104 also decreases as it approaches the substrate 102 from the interface 105. From the above, it was confirmed that the diffusion layer 106 contains zinc, which is the first metal element, and also contains silicon, which is the first element, and copper, which is the second metal element. Furthermore, in the diffusion layer 106, the concentration plots of silicon and copper with respect to depth intersect with each other. From this, it was found that the diffusion layer 106 contains at least one of the first element and the second metal element in addition to the first metal element in any region.

[0056] 2. Example 2 In this example, the effect of the diffusion layer 106 on the adhesive strength between the substrate 102 and the first metal film 104 was evaluated.

[0057] Electricity was supplied to the first metal film 104 of the wiring board 100 produced in Example 1, and a copper film (thickness 3 μm) was formed as the second metal film 108 by electrolytic plating. In this example, the thickness of the first intermediate layer 120 was set to 15 nm, and the heating temperature after the formation of the second metal film 108 was changed to evaluate the effect of the diffusion layer 106. Samples 8 to 10, i.e., wiring boards not provided with the diffusion layer 106, were also evaluated as comparative examples.

[0058] The effect of the diffusion layer 106 on the adhesion between the first metal film 104 and the substrate 102 was evaluated by a tape peel test and an etching test. The former was evaluated by attaching a polyimide-based adhesive tape (manufactured by Nitto Denko Corporation, model number: heat-resistant insulating polyimide adhesive tape No. 360UL) to the second metal film 108, peeling the adhesive tape, and visually observing the adhesive tape. The latter was evaluated by etching the wiring substrate 100 and visually checking whether the first metal film 104 or the second metal film 108 peeled off during the etching. The etching was performed using 1% ammonium persulfate as an etchant at 23° C. for 1 minute.

[0059] The results are shown in Table 1. As shown in Table 1, when the diffusion layer 106 having the structure shown in the present disclosure is used, if the heating temperature after the formation of the second metal film 108 is 250° C. or higher (sample numbers 3 to 7), peeling is not observed in the tape peel test, and it was found that the first metal film 104 and the second metal film 108 remain on the substrate 102. Also, if the heating temperature is 350° C. or higher (sample numbers 4 to 7), peeling is not observed in either the tape peel test or the etching test. On the other hand, in the comparative example (sample number 8) in which the diffusion layer 106 is not used, that is, in the case in which the first intermediate layer 120 is not formed on the substrate 102, peeling is observed in the tape peel test even if the heating temperature after the formation of the second metal film 108 is 450° C. These results clearly show that when the diffusion layer 106 of the present disclosure is not provided, the adhesion between the first metal film 104 and the substrate 102 is poor, and the first metal film 104 and the second metal film 108 easily peel off from the substrate 102, whereas by providing the diffusion layer 106 of the present disclosure, metal wiring can be formed on the substrate 102 with strong adhesion.

[0060] Here, when the surface roughness of the substrate increases, an anchor effect is exerted, and therefore adhesion to a metal film formed thereon is usually improved. However, even when the surface roughness of the substrate 102 is 200 nm, peeling is observed in a tape peel test (sample 9), and it was confirmed from the results of sample 10 that a rough surface with a surface roughness of 1000 nm is necessary when the diffusion layer 106 is not provided. However, when the diffusion layer 106 is provided as thick as 1000 nm, fine processing becomes difficult as described above, and it is extremely disadvantageous to form wiring with a line-space (L / S) of 10 μm / 10 μm, for example. Therefore, by using the diffusion layer 106 of the present disclosure, it becomes possible to form wiring that has been subjected to fine processing on a substrate having a surface roughness to such an extent that an anchor effect is not expected, that is, a substrate having an extremely high surface flatness. This contributes to the manufacture of wiring substrates such as high-frequency circuit substrates that require high flatness of wiring.

[0061] [Table 1]

[0062] The above-described embodiments of the present disclosure may be combined as appropriate as long as they are not mutually inconsistent. In addition, a product in which a person skilled in the art appropriately adds or deletes components or modifies the design based on each embodiment is also included in the scope of the present disclosure as long as it includes the gist of the present disclosure.

[0063] Furthermore, even if there are other effects and advantages different from those brought about by the above-described embodiments, those that are clear from the description in this specification or that can be easily predicted by a person skilled in the art are naturally understood to be brought about by the present disclosure. [Explanation of symbols]

[0064] 100: wiring board, 100-1: wiring board, 100-2: wiring board, 100-3: wiring board, 100-4: wiring board, 100-5: wiring board, 102: board, 102-1: board, 102-2: board, 102a: concentration of first element, 103: interface, 104: first metal film, 104-1: metal film, 104a: concentration of second metal element, 105: interface, 106: diffusion layer, 106a: concentration of first metal element, 106b: region, 106c: region, 108: second metal film, 110: through hole, 112: filling material, 120: first intermediate layer, 122: second intermediate layer, 124: resist mask, 130: semiconductor device, 132: main board, 133: central processing unit, 134: connection wiring, 136: bump, 136-1: bump, 136-2: bump, 136-3: bump, 138: terminal, 140: interlayer insulating layer, 141: interlayer insulating layer, 150: semiconductor device, 160: semiconductor device, 162-1: semiconductor chip, 162-2: semiconductor chip, 164: terminal, 166: terminal, 168: bump, 170: wire wiring

Claims

1. a substrate comprising a first element; a diffusion layer in contact with the substrate and including a first metal element; a first metal film in contact with the diffusion layer and containing a second metal element; and a second metal film located on the first metal film and in contact with the first metal film; The diffusion layer has a thickness of 1 nm or more and 10 nm or less, the first element, the first metal element, and the second metal element coexist in the diffusion layer; The substrate has a through hole, the diffusion layer, the first metal film, and the second metal film continuously cover the upper and lower surfaces of the substrate and the sidewalls of the through holes.

2. the concentration of the second metal element in the diffusion layer decreases toward the substrate in a thickness direction; The wiring board according to claim 1 , wherein a concentration of the first element in the diffusion layer decreases toward the first metal film in the thickness direction.

3. 3. The wiring board according to claim 2, wherein there is a region in the diffusion layer where a plot of the concentration of the second metal element versus the thickness of the diffusion layer intersects with a plot of the concentration of the first element versus the thickness.

4. the first element is silicon; The wiring board according to claim 1 , wherein the second metal element is selected from the group consisting of copper, titanium, chromium, nickel, and gold.

5. The wiring board according to claim 4 , wherein the first metal element is selected from the group consisting of zinc, titanium, zirconium, aluminum, and tin.

6. The wiring board according to claim 1 , wherein the first metal element is present as an oxide in the diffusion layer.

7. The wiring substrate according to claim 1 , wherein the substrate is selected from a glass substrate, a quartz substrate, a semiconductor substrate, and a ceramic substrate.

8. an insulating layer located on the diffusion layer, the first metal film, and the second metal film, the insulating layer having an opening overlapping the through hole; and The wiring board according to claim 1 , further comprising a first wiring located in the opening.

9. The wiring board according to claim 8 , further comprising a second wiring on said first wiring and electrically connected to said first wiring.

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