Glass laminate, method for manufacturing a glass laminate, and semiconductor device.

Abstract

The present invention provides a glass laminate capable of suppressing cracks and delamination occurring in the glass substrate and metal layer, and a method for manufacturing the same. [Solution] The glass laminate 10 comprises a glass substrate 1, a metal oxide layer 2 disposed on the surface of the glass substrate 1, and a metal layer 3 disposed on the surface of the metal oxide layer 2 opposite to the glass substrate, wherein the metal oxide layer 2 contains halogen atoms.

Description

[Technical Field]

[0001] This disclosure relates to a glass laminate, a method for manufacturing a glass laminate, and a semiconductor device. [Background technology]

[0002] Recently, 2.5D packages (2.5-dimensional packaging) have been applied to HPC (High-Performance Computing). Furthermore, in recent years, with the demand for higher speed and lower costs, substrates with high-density fine wiring, such as FOPLP (Fan-Out Panel Level Package), have been actively developed. High-density fine wiring substrates are mounted on various electronic devices such as smartphones and large-scale servers. For example, in the case of application to large-scale servers, this high-density fine wiring substrate is used as an interposer, on which different types of LSIs such as CPUs and memory are mounted, and this substrate is then mounted on a motherboard. Silicon interposers have been used for such high-density fine wiring substrates, but from the perspective of reducing the difference in thermal expansion coefficients with the wiring material, glass interposers that use a glass substrate as the core material and have through-electrodes penetrating the core material are attracting attention.

[0003] Reflow soldering is sometimes performed when mounting semiconductor elements onto a glass interposer or when connecting a glass interposer to a motherboard. During high-temperature processes such as reflow soldering, the difference in thermal expansion coefficients between the glass substrate and the metal layers constituting the conductive layer or through-electrode formed on the glass substrate can cause cracks in the glass substrate and metal layers, or delamination between the glass substrate and the metal layers. Therefore, it has been proposed to place an adhesion layer between the glass substrate and the metal layer to improve adhesion.

[0004] For example, Patent Document 1 discloses a method including the steps of depositing an adhesive layer containing manganese oxide (MnOx) on the surface of a glass or glass-ceramic substrate, depositing a catalyst for electroless copper deposition on the adhesive layer, depositing a first copper layer by electroless plating on the MnOx layer after depositing the catalyst, and annealing the adhesive layer in a reducing atmosphere.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, even if an adhesion layer is provided between the glass substrate and the metal layer, the adhesion layer cannot sufficiently absorb stress strain, and cracks and peeling of the glass substrate and the metal layer cannot be sufficiently reduced.

[0007] The present disclosure is an invention made in view of the above circumstances, and the main object thereof is to provide a glass laminate capable of suppressing cracks and peeling that occur in a glass substrate and a metal layer.

Means for Solving the Problems

[0008] One embodiment of the present disclosure provides a glass laminate having a glass substrate, a metal oxide layer disposed on the surface of the glass substrate, and a metal layer disposed on a surface of the metal oxide layer opposite to the glass substrate, wherein the metal oxide layer contains a halogen atom.

[0009] Other embodiments of the present disclosure are methods for manufacturing the glass laminate described above, including a metal oxide layer forming step of forming the metal oxide layer on the surface of the glass substrate by atomic layer deposition, and a metal layer forming step of forming the metal layer on the surface of the metal oxide layer opposite to the glass substrate. The metal oxide layer forming step includes supplying a source gas containing a metal halide, adsorbing the metal halide on the surface of the glass substrate, performing a first exhaust process to exhaust excess source gas, supplying an oxidizing agent, oxidizing the metal halide, and performing a second exhaust process to exhaust excess oxidizing agent. By repeating these steps as one cycle, a metal oxide layer containing the halogen atom is formed, providing a method for manufacturing a glass laminate.

[0010] Other embodiments of the present disclosure provide a semiconductor device including a through-electrode substrate including the glass laminate described above, an element disposed on one surface side of the through-electrode substrate and electrically connected to the through-electrode layer, and a wiring substrate disposed on the other surface side of the through-electrode substrate and electrically connected to the through-electrode layer.

Advantages of the Invention

[0011] In the present disclosure, there is an effect that a glass laminate capable of suppressing cracks and peeling occurring in the glass substrate and the metal layer can be provided.

Brief Description of the Drawings

[0012] [Figure 1] It is a schematic cross-sectional view illustrating the glass laminate in the present disclosure. [Figure 2] It is a schematic cross-sectional view illustrating the glass laminate in the present disclosure. [Figure 3] It is a schematic cross-sectional view illustrating the cross-sectional shape of the through-hole of the glass substrate. [Figure 4] It is a profile obtained by measuring the concentration of chlorine atoms in the thickness direction of the TiOx layer by dynamic secondary ion mass spectrometry. [Figure 5] It is a schematic cross-sectional view illustrating the semiconductor device in the present disclosure. [Figure 6] This is a schematic cross-sectional view illustrating a through-electrode substrate in this disclosure. [Figure 7] This is a schematic cross-sectional view of a glass laminate fabricated in an experimental example. [Modes for carrying out the invention]

[0013] Embodiments of this disclosure will be described below with reference to drawings and other figures. However, this disclosure can be implemented in many different ways and should not be interpreted as being limited to the embodiments described below. In addition, the drawings may be schematically represented in terms of width, thickness, shape, etc. of each part compared to the actual form in order to make the explanation clearer, but these are merely examples and should not limit the interpretation of this disclosure. Furthermore, in this specification and each figure, elements similar to those described above with respect to previously shown figures will be denoted by the same reference numerals, and detailed explanations may be omitted as appropriate.

[0014] In this specification, when describing a configuration in which one member is placed on top of another member, unless otherwise specified, the terms "on top" or "below" include both cases: one in which the other member is placed directly above or below the other member so as to be in contact with it, and another in which the other member is placed above or below the other member via yet another member. Similarly, when describing a configuration in this specification in which one member is placed on the surface of another member, unless otherwise specified, the terms "on the surface" or "on the surface" include both cases: one in which the other member is placed directly above or below the other member so as to be in contact with it, and another in which the other member is placed above or below the other member via yet another member.

[0015] The glass laminate, the method for manufacturing the glass laminate, and the semiconductor device of the present invention will be described in detail below.

[0016] A. Glass laminate The glass laminate in this disclosure comprises a glass substrate, a metal oxide layer disposed on the surface of the glass substrate, and a metal layer disposed on the surface of the metal oxide layer opposite to the glass substrate, wherein the metal oxide layer contains halogen atoms.

[0017] Figures 1 and 2 are schematic cross-sectional views showing an example of a glass laminate in this disclosure. As shown in Figure 1, the glass laminate 10 includes a glass substrate 1, a metal oxide layer 2 disposed on the surface of the glass substrate 1, and a metal layer 3 disposed on the surface of the metal oxide layer 2 opposite to the glass substrate 1. In this disclosure, the metal oxide layer 2 contains halogen atoms.

[0018] As shown in Figure 1, the glass substrate 1 may be provided with a through hole X that penetrates in the thickness direction. In this case, as shown in Figure 1, it is preferable that at least a metal oxide layer 2 and a metal layer 3 are arranged on the side walls of the through hole X. The metal layer 3 arranged on the side walls of the through hole X reaches the first main surface S1 and the second main surface S2 of the glass substrate 1, thereby constituting a through electrode layer 31. The metal layer 3 may also have a through electrode layer 31 and a conductive layer 32 formed on at least one of the first main surface S1 and the second main surface S2 of the glass substrate 1.

[0019] On the other hand, as shown in Figure 2, the glass substrate 1 does not have to have through holes. In this case, for example, it is preferable that the metal oxide layer 2 and the metal layer 3 are arranged in this order from the glass substrate 1 side on at least one of the first main surface S1 and the second main surface S2 of the glass substrate 1.

[0020] During high-temperature processes such as reflow soldering in the manufacturing of semiconductor devices, delamination and cracking may occur due to differences in the coefficients of thermal expansion between the glass substrate and the metal layer. Furthermore, when semiconductor devices are used in high-temperature environments, a large difference in the coefficients of thermal expansion between the glass substrate and the metal layer increases the likelihood of cracking and delamination.

[0021] According to this invention, a metal oxide layer 2 is placed between the glass substrate 1 and the metal layer 3, and furthermore, the metal oxide layer 2 contains halogen atoms, which improves the flexibility (bendability) of the metal oxide layer 2. This allows it to absorb stress and strain caused by the expansion and contraction of the glass substrate and the metal layer, thereby suppressing cracks and delamination of the glass substrate and the metal layer. This is thought to be due to the following reasons.

[0022] The metal oxide layer has MOM bonds (where M is the metal). The inclusion of halogen atoms in the metal oxide layer partially introduces MX bonds (where X is the halogen atom) into the MOM bonds. This partially breaks the MOM bonds in the metal oxide layer, reducing its rigidity and improving its flexibility. This allows it to absorb (mitigate) stress and strain caused by the expansion and contraction of the glass substrate and metal layer during heating and cooling.

[0023] The glass laminates described in this disclosure will be explained below for each component.

[0024] 1. Metal oxide layer The metal oxide layer in this disclosure is provided between the glass substrate and the metal layer and functions as an adhesion layer to improve the adhesion between the glass substrate and the metal layer. The metal oxide layer is usually in direct contact with the glass substrate and the metal layer. The metal oxide layer only needs to be located on at least a portion of the surface of the glass substrate. If the glass substrate has through holes, it is preferable that the metal oxide layer is located at least on the side walls of the through holes.

[0025] The metal oxide layer contains a metal oxide as its main component. The metal oxide is not particularly limited as long as it improves the adhesion between the glass substrate and the metal layer, and examples include titanium oxide, zinc oxide, manganese oxide, nickel oxide, aluminum oxide, tin oxide, iron oxide, indium oxide, and copper oxide. Among these, titanium oxide (TiOx) is preferred.

[0026] The metal oxide layer contains halogen atoms. "The metal oxide layer contains halogen atoms" means that when the atomic concentration in the depth direction of the metal oxide layer is measured by the dynamic secondary ion mass spectrometry (D-SIMS) method described later, halogen atoms are detected. Examples of the halogen atoms include chlorine atoms, fluorine atoms, bromine atoms, etc., and among them, chlorine atoms are preferable.

[0027] As a method for forming a metal oxide layer containing halogen atoms, an atomic layer deposition method (ALD method) using a source gas containing a metal halide, which is described in "B. Method for manufacturing a glass laminate", can be mentioned. In the present disclosure, the metal oxide layer is preferably an atomic layer deposition film formed by the atomic layer deposition method. Generally, when forming a metal oxide layer by the atomic layer deposition method, since the oxidation treatment with an oxidizing agent is sufficiently performed, the metal oxide layer does not contain halogen atoms. However, by adjusting the oxidation treatment time of the oxidation treatment in the atomic layer deposition method, a metal oxide layer containing halogen atoms can be obtained.

[0028] The content of halogen atoms in the metal oxide layer is, for example, 1×10 15 atm / cm 3 or more, and preferably 1×10 16 atm / cm 3 or more, and more preferably 1×10 17 atm / cm 3 or more. When the content of halogen atoms is within the above range, the flexibility of the metal oxide layer becomes further better. Therefore, cracks and peeling of the glass substrate and the metal layer can be further suppressed. On the other hand, the content of halogen atoms in the metal oxide layer is preferably 1×10 23 atm / cm 3 or less, more preferably 1×10 22 atm / cm 3 or less, still more preferably 1×10 21 atm / cm 3 or less, and most preferably 1×10 20 atm / cm 3The following is particularly preferable. Too much halogen atom content can accelerate wiring corrosion and increase resistivity. Specifically, the halogen atom content in the metal oxide layer should be, for example, 1 × 10⁻⁶. 15 atm / cm 3 The above 1 x 10 23 atm / cm 3 The following is true: 1 × 10 16 atm / cm 3 The above 1 x 10 23 atm / cm 3 The following is preferable: 1 × 10 17 atm / cm 3 The above 1 x 10 23 atm / cm 3 The following is more preferable: 1 × 10 17 atm / cm 3 The above 1 x 10 21 atm / cm 3 The following is even more preferable: 1 × 10 17 atm / cm 3 The above 1 x 10 20 atm / cm 3 The following are particularly preferable.

[0029] In this disclosure, the halogen atom content in the metal oxide layer is determined by the halogen atom content at the center of the thickness direction of the metal oxide layer.

[0030] The halogen atom content in the thickness direction of the metal oxide layer was determined using a dynamic secondary ion mass spectrometer (D-SIMS) to measure a sample obtained by forming a metal oxide layer on a glass substrate, and the Cs + The halogen atom content is determined by measuring the halogen atom content in the depth direction using dynamic secondary ion mass spectrometry while sequentially sputtering the metal oxide layer from the surface using ions. A PHI ADEPT1010 (manufactured by ULVAC, Inc.) can be used as the dynamic secondary ion mass spectrometer.

[0031] (Measurement conditions) During the measurement, the primary ion was Cs + Select the option, and choose negative ions for the polarity of the secondary ions. The other measurement conditions are as follows. • Primary acceleration voltage: 1.0kV • Detection area: 90 × 90 (μm × μm)

[0032] Figure 4 shows a profile of the chlorine atom concentration in the thickness direction of the TiOx layer, which is a metal oxide layer, measured by dynamic secondary ion mass spectrometry. In this profile, the left end in the horizontal axis direction is the surface of the metal oxide layer, and the right end is the glass substrate side. The thickness of the metal oxide layer is the distance from the surface of the metal oxide layer to the charge-up point.

[0033] As described above, the halogen atom content in the metal oxide layer is determined by the halogen atom content at the center of the metal oxide layer in the thickness direction. Since the thickness of the metal oxide layer (TiOx layer) obtained from Figure 4 is approximately 8.57 nm, the center of the metal oxide in the thickness direction is located approximately 4.29 nm away from the interface (charge-up position) between the metal oxide layer and the glass substrate. Therefore, the concentration of chlorine atoms at the center of this metal oxide layer (TiOx layer) in the thickness direction is approximately 1 × 10⁻⁶. 20 atm / cm 3 That is the case.

[0034] The thickness of the metal oxide layer is, for example, 5 nm or more, may be 7 nm or more, or 10 nm or more. On the other hand, the thickness of the metal oxide layer is, for example, 50 nm or less, may be 40 nm or less, or 30 nm or less. The thickness of the metal oxide layer is defined as the distance from the surface of the metal oxide layer to the charge-up in the depth profile obtained by dynamic secondary ion mass spectrometry, as described above.

[0035] 2. Glass substrate As shown in Figures 1 and 2, the glass substrate 1 in this disclosure has a first main surface S1 and a second main surface S2 facing the first main surface S1.

[0036] As shown in Figure 1, the glass substrate 1 preferably has through holes X that penetrate in the thickness direction. The metal oxide layer in this disclosure is formed by atomic layer deposition (ALD). Compared to other methods for forming metal oxide layers, such as vapor deposition and sputtering, atomic layer deposition makes it possible to form a metal oxide layer with a uniform thickness on the side walls of the through holes. When the thickness of the metal oxide layer is uniform, the adhesion between the glass substrate and the metal layer is further improved. Therefore, by using a glass substrate having through holes, the effects of the present invention can be significantly obtained.

[0037] Examples of glass used in glass substrates include alkali-free glass, borosilicate glass, and quartz.

[0038] The thermal expansion coefficient of the glass substrate is preferably, for example, 2 ppm / °C to 9 ppm / °C. If the thermal expansion coefficient of the glass substrate is within the above range, the difference between the thermal expansion coefficient of the glass substrate and the thermal expansion coefficient of the element can be sufficiently reduced. In this specification, the thermal expansion coefficient is the linear expansion coefficient. The thermal expansion coefficient of the glass substrate is a value measured by thermomechanical analysis (TMA) in accordance with JIS R3102:1995. The thermal expansion coefficient of the glass substrate is the average linear expansion coefficient from 30°C to 260°C.

[0039] The planar shape of the glass substrate is not particularly limited, but examples include rectangles, squares, and other rectangular shapes. The size of the glass substrate is not particularly limited, but if the glass substrate is rectangular, the length of the diagonal is, for example, 70 mm or more and 1000 mm or less, and may also be 90 mm or more and 800 mm or less, or 100 mm or more and 700 mm or less.

[0040] When a glass substrate has through holes, the plan view shape of the through holes is, for example, approximately circular.

[0041] Figures 3(a) to 3(e) are schematic cross-sectional views illustrating the cross-sectional shape of a through-hole in a glass substrate. Examples of cross-sectional shapes of the through-hole X in the glass substrate 1 include a straight shape as shown in Figure 3(a), an inverse tapered shape as shown in Figure 3(b) where the opening diameter on the first main surface S1 side is larger than the opening diameter on the second main surface S2 side, a forward tapered shape as shown in Figure 3(c) where the opening diameter on the first main surface S1 side is smaller than the opening diameter on the second main surface S2 side, an hourglass shape as shown in Figure 3(d) which includes a portion where the diameter is smallest at a predetermined position between the first main surface S1 and the second main surface S2, and a bowing shape as shown in Figure 3(e) where the diameter is largest at a predetermined position between the first main surface S1 and the second main surface S2.

[0042] The thickness of the glass substrate is, for example, 100 μm or more, but may also be 200 μm or more, 300 μm or more, or 400 μm or more. By having the glass substrate thickness within the above range, it is possible to suppress excessive deflection of the glass substrate. This prevents difficulties in handling the glass substrate during the manufacturing process, and prevents the glass substrate from warping due to internal stresses such as thin films placed on the first or second main surface of the glass substrate. On the other hand, the thickness of the glass substrate is, for example, 2000 μm or less, but may also be 1000 μm or less, or 800 μm or less. If the thickness of the glass substrate is within the above range, the time required for the process of forming through holes in the glass substrate can be shortened. Specifically, the thickness of the glass substrate is 100 μm or more and 2000 μm or less, but may also be 200 μm or more and 1000 μm or less, 300 μm or more and 1000 μm or less, or 400 μm or more and 800 μm or less.

[0043] 3. Metal layer In this disclosure, the metal layer is located on the surface opposite to the glass substrate of the metal oxide layer.

[0044] As shown in Figure 1, when the glass substrate 1 has a through hole X, it is preferable that the metal layer 3 has a through electrode layer 31. The through electrode layer 31 is located on the surface of the metal oxide layer 2, which is positioned on the side wall of the through hole X, opposite to the side wall of the through hole X, and extends from the first main surface S1 to the second main surface S2 of the glass substrate 1, thereby enabling the first main surface and the second main surface of the glass substrate to be electrically connected.

[0045] In this disclosure, the through-electrode layer is preferably a so-called conformal via, which is arranged only on the side wall of the through-hole in the glass substrate, and there is a space inside the through-hole where no through-electrode exists. In this case, a hollow portion may be arranged inside the through-hole, or the inside of the through-hole may be filled with a resin portion.

[0046] As shown in Figures 1 and 2, the metal layer 3 may have a conductive layer 32 disposed on at least one of the first main surface and the second main surface of the glass substrate 1. The conductive layer 32 is disposed on at least one of the first main surface S1 and the second main surface S2 of the glass substrate 1 via a metal oxide layer 2. As shown in Figure 1, if the metal layer 3 has a through electrode layer 31, the conductive layer 32 may be electrically connected to the through electrode layer 31.

[0047] The material of the metal layer is not particularly limited as long as it is a conductive material, and conductive materials commonly used for through electrodes or wiring can be used. Examples of conductive materials include metals such as copper, gold, silver, platinum, rhodium, tin, aluminum, nickel, and chromium, or alloys containing these metals. In this disclosure, the conductive material is preferably copper.

[0048] The thermal expansion coefficient of the conductive material constituting the metal layer is not particularly limited, but may be, for example, 12 ppm / °C or higher, and may be 15 ppm / °C or higher. On the other hand, the thermal expansion coefficient of the conductive material constituting the metal layer may be, for example, 20 ppm / °C or lower, and may be 18 ppm / °C or lower.

[0049] The method for forming the metal layer is not particularly limited. For example, the metal layer may be formed by physical deposition methods such as vapor deposition or sputtering, or by chemical deposition or plating.

[0050] The metal layer may be a single layer or a multilayer formed by stacking multiple layers. For example, the metal layer may have a seed layer positioned on the metal oxide layer side (glass substrate side) and a plating layer positioned on the side of the seed layer opposite to the metal oxide layer side (glass substrate side). The material for the seed layer can be appropriately selected from materials commonly used for seed layers in general plating methods, such as titanium, molybdenum, tungsten, tantalum, nickel, chromium, aluminum, compounds thereof, and alloys thereof. The material for the plating layer can be, for example, the same material as the metal layer described above.

[0051] The thickness of the metal layer may be, for example, 0.1 μm or more, but may also be 0.5 μm or more, 1 μm or more, 3 μm or more, or 5 μm or more. On the other hand, the thickness of the metal layer may be, for example, 20 μm or less, or 15 μm or less. The thickness of the metal layer may be, for example, 0.1 μm or more and 20 μm or less, 0.5 μm or more and 15 μm or less, 1 μm or more and 15 μm or less, 3 μm or more and 15 μm or less, or 5 μm or more and 15 μm or less. For example, when the metal layer is formed by a sputtering method, a relatively thin metal layer can be obtained. Also, for example, when the metal layer is formed by a plating method, a relatively thick metal layer can be obtained.

[0052] In this specification, the thickness of the metal layer is measured based on cross-sectional images of the through-electrode substrate taken using a scanning electron microscope (SEM). The thickness is the arithmetic mean of the thicknesses at any five locations.

[0053] 4.Applications The applications of the glass laminate in this disclosure are not particularly limited, but it can be used as a substrate for an interposer.

[0054] B. Method for manufacturing glass laminates The method for manufacturing a glass laminate in this disclosure is a method for manufacturing a glass laminate as described above, comprising: a metal oxide layer formation step of forming the metal oxide layer on the surface of the glass substrate by atomic layer deposition; and a metal layer formation step of forming the metal layer on the surface of the metal oxide layer opposite to the glass substrate, wherein the metal oxide layer formation step is performed by repeatedly carrying out, as one cycle, an adsorption treatment in which a raw material gas containing a metal halide is supplied and the metal halide is adsorbed onto the surface of the glass substrate, a first exhaust treatment in which the excess raw material gas is exhausted, an oxidation treatment in which an oxidizing agent is supplied and the metal halide is oxidized, and a second exhaust treatment in which the excess oxidizing agent is exhausted, thereby forming the metal oxide layer containing the halogen atoms.

[0055] According to the method for manufacturing a glass laminate in this disclosure, a glass laminate can be obtained that can suppress cracks and delamination occurring in the glass substrate and metal layer for the reasons described above.

[0056] The manufacturing method for the glass laminate described in this disclosure will be explained step by step below.

[0057] 1. Metal oxide layer formation process This process involves forming a metal oxide layer on the surface of a glass substrate by atomic layer deposition. This process consists of supplying a raw material gas containing metal halides and performing an adsorption treatment to adsorb the metal halides onto the surface of the glass substrate, followed by a first exhaust treatment to exhaust the excess raw material gas, followed by an oxidation treatment to supply an oxidizing agent and oxidize the metal halides, followed by a second exhaust treatment to exhaust the excess oxidizing agent. This cycle is repeated to form the metal oxide layer containing halogen atoms.

[0058] Atomic layer deposition (ALD) is a film deposition method that uses an atomic layer deposition apparatus (ALD apparatus) to alternately supply a metal-containing raw material gas and an oxidizing agent to a reaction chamber where the target object is placed, thereby creating a layer containing metal oxides on the surface of the object. In atomic layer deposition, a self-stopping mechanism is in operation, so the metal is deposited on the surface of the object in atomic layer units. Therefore, one cycle consists of adsorption treatment of the metal raw material by supplying the raw material gas, a first exhaust treatment to exhaust excess raw material gas, oxidation treatment of the metal raw material by supplying the oxidizing agent and a second exhaust treatment to exhaust excess oxidizing agent, and the thickness of the layer produced can be controlled by the number of cycles.

[0059] (1) Adsorption treatment This process involves supplying a raw material gas containing a metal halide and adsorbing (chemiadsorption) the metal halide onto the surface of a glass substrate. In other words, the hydroxyl groups on the surface of the glass substrate react with the metal halide. Furthermore, it is preferable to create the metal oxide layer in a reaction chamber under reduced pressure before film formation. The pressure in the reaction chamber is preferably reduced to, for example, 10 hPa or less, and may also be 5 hPa or less.

[0060] The metal in the metal halide is the same as the metal in the metal oxide layer described in "A. Glass Laminate 1. Metal Oxide Layer" above. The halogen atom in the metal halide is the same as the halogen atom described in "A. Glass Laminate 1. Metal Oxide Layer" above. Among these, TiCl4 is preferred as the metal halide.

[0061] The raw material gas may contain one or more metal halides.

[0062] Regarding film deposition, for example, the process is carried out while an inert gas is flowed through the reaction chamber at a constant flow rate. Examples of inert gases used include N2 and Ar. The flow rate of the inert gas is, for example, between 1 sccm and 200 sccm.

[0063] The time for supplying the raw material gas to adsorb the metal raw material is, for example, between 0.01 seconds and 1.0 second.

[0064] (2) First exhaust treatment After the adsorption treatment, excess raw material gas is purged. This removes the phytoadsorbed raw material gas from the surface of the glass substrate. It is preferable to purge the excess raw material gas by flowing an inert gas. Examples of inert gases used include N2 and Ar. The flow rate of the inert gas when purging the excess raw material gas is, for example, between 1 sccm and 200 sccm. The time for purging the excess raw material gas is, for example, between 10 seconds and 180 seconds.

[0065] (3) Oxidation treatment This process involves supplying an oxidizing agent to oxidize the metal halide.

[0066] The time for supplying the oxidizing agent to oxidize the adsorbed metal raw material is, for example, 0.1 seconds or more and 1.0 second or less, and may be 0.01 seconds or more and 10.0 seconds or less. Shortening the supply time of the oxidizing agent increases the content of halogen atoms in the metal oxide layer. On the other hand, lengthening the supply time of the oxidizing agent decreases the content of halogen atoms in the metal oxide layer. In this disclosure, by adjusting the supply time of the oxidizing agent, the content of halogen atoms in the metal oxide layer can be increased to 1 × 10⁻⁶. 17 atm / cm 3 The above 1 x 10 23 atm / cm 3 The following adjustments are preferable. As an oxidizing agent, for example, H2O, O2 plasma, O3, etc., can be used, but among these, H2O is preferred.

[0067] (4) Second exhaust treatment After the adsorption treatment, it is preferable to purge the excess oxidizing agent. Purging of the excess oxidizing agent is performed by flowing an inert gas. N2, Ar, etc., can be used as the inert gas. The flow rate of the inert gas when purging the excess oxidizing agent can be the same as the flow rate of the inert gas when purging the excess raw material gas. The time for purging the excess oxidizing agent is, for example, 10 seconds or more and 180 seconds or less.

[0068] When depositing layers using atomic layer deposition, the deposition temperature can be set to, for example, between 30°C and 300°C. This makes it easier to control the chemical reactions that occur when the metal oxide layer is fabricated, enabling the stable deposition of the metal oxide layer.

[0069] 2.Metal layer formation process This process involves forming a metal layer on the surface of the metal oxide layer opposite to the glass substrate. The method for forming the metal layer is described in detail in "A. Glass Laminate 3. Metal Layer" above, so the explanation is omitted here.

[0070] 3. Glass laminate The glass laminates manufactured in this disclosure are described in detail in "A. Glass Laminates" above, so a detailed explanation is omitted here.

[0071] C. Semiconductor Equipment This disclosure provides a semiconductor device comprising: a through-electrode substrate having the glass laminate described above; an element disposed on one side of the through-electrode substrate and electrically connected to the through-electrode layer; and a wiring substrate disposed on the other side of the through-electrode substrate and electrically connected to the through-electrode layer.

[0072] Figure 5 is a schematic cross-sectional view illustrating a semiconductor device in this disclosure, and Figure 6 is a schematic cross-sectional view illustrating a through-electrode substrate used in the semiconductor device shown in Figure 5.

[0073] As shown in Figure 5, the semiconductor device 100 of this disclosure includes a through-electrode substrate 20 having the glass laminate described above, an element 30 disposed on one side of the through-electrode substrate 20 and electrically connected to the through-electrode layer, and a wiring substrate 40 disposed on the other side of the through-electrode substrate 20 and electrically connected to the through-electrode layer.

[0074] The through-electrode substrate 20 shown in Figure 6 comprises the glass laminate 10 described above, a plurality of first insulating layers 11a arranged on the first main surface S1 side of the glass substrate 1, and a second conductive layer 12a arranged between each first insulating layer 11a and electrically connected to the metal layer 3 (through-electrode layer 31 and first conductive layer 32) in the glass laminate 10. The second conductive layer 12a and the first conductive layer 32 are electrically connected via 13. Furthermore, the through-electrode substrate 20 comprises a plurality of second insulating layers 11b arranged on the second main surface S2 side of the glass substrate 1, and a third conductive layer 12b arranged between each second insulating layer 11b and electrically connected to the metal layer 3 (through-electrode layer 31 and first conductive layer 32) in the glass laminate 10. The third conductive layer 12b and the first conductive layer 32 are electrically connected via 13. Note that the conductive layers in the glass laminate may also be referred to as the first conductive layers.

[0075] In the semiconductor device 100 shown in Figure 5, the through-electrode layer on the through-electrode substrate 20 and the element 30 are electrically connected by a first junction 15. Furthermore, the through-electrode layer on the through-electrode substrate 20 and the wiring substrate 40 are electrically connected by a second junction 25.

[0076] The semiconductor device in this disclosure has a through-electrode substrate comprising the glass laminate described above, and therefore is a highly reliable semiconductor device.

[0077] 1. Through-electrode substrate As shown in Figure 5, in the semiconductor device 100, the through-electrode substrate 20 having the glass laminate 10 described above functions as an interposer.

[0078] As shown in Figure 6, the through-electrode substrate 20 has the glass laminate 10 described above. The glass laminate 10 included in the through-electrode substrate 20 has a glass substrate 1 with through holes X, and a metal layer 3 that includes a through-electrode layer 31. A metal oxide layer 2 is formed between the through-electrode layer 31 and the glass substrate 1.

[0079] The through-electrode substrate 20 preferably has a plurality of first insulating layers 11a arranged on the first main surface S1 side of the glass substrate 1, and a plurality of second insulating layers 11b arranged on the second main surface S2 side of the glass substrate 1. Furthermore, the through-electrode substrate 20 preferably has a second conductive layer 12a arranged between each first insulating layer 11a and electrically connected to the metal layer 3 (through-electrode layer 31 and first conductive layer 32) in the glass laminate 10. Furthermore, it is preferable to have a third conductive layer 12b arranged between each second insulating layer 11b and electrically connected to the metal layer 3 (through-electrode layer 31 and first conductive layer 32) in the glass laminate 10.

[0080] The materials for the first and second insulating layers are preferably insulating resins. Examples of insulating resins include polyimide, polyamide, polyamide-imide, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polyetheretherketone, polyethersulfone, polycarbonate, polyetherimide, epoxy resin, phenolic resin, polyphenylene ether, acrylic resin, polyolefin, polycycloolefin, and liquid crystalline polymer compounds. Examples of polyolefins include polyethylene and polypropylene. Examples of polycycloolefins include polynorbornene. From the viewpoint of good heat resistance and processability, epoxy resin and polyimide are preferred. The materials for the multiple first and second insulating layers may be the same or different from each other.

[0081] The number of layers in the first insulating layer and the second insulating layer is two or more, preferably three or more, and more preferably four or more. On the other hand, the number of layers in the first insulating layer and the second insulating layer is preferably 10 or less, more preferably 8 or more, and particularly preferably 7 or less.

[0082] The thickness of the first insulating layer and the second insulating layer may be, for example, 1.5 μm or more, or 2.5 μm or more. On the other hand, the thickness of the first insulating layer and the second insulating layer may be, for example, 25 μm or less. The thickness of the first insulating layer may be, for example, 1.5 μm or more and 25 μm or less, or 2.5 μm or more and 25 μm or less.

[0083] Examples of methods for forming the first and second insulating layers include photolithography and printing.

[0084] The materials for the second and third conductive layers are not particularly limited as long as they are conductive materials; conductive materials commonly used for wiring in interposers can be used.

[0085] The thickness of the second conductive layer and the third conductive layer may be, for example, 0.1 μm or more, or 5 μm or more. On the other hand, the thickness of the second conductive layer and the third conductive layer may be, for example, 20 μm or less, or 15 μm or less. The method for forming the second conductive layer and the third conductive layer may be an additive method or a subtractive method.

[0086] The material used for the via is not particularly limited as long as it is conductive; general conductive materials used for vias can be used, and the material can be appropriately selected depending on the via's shape, formation method, etc.

[0087] 2. Elements Examples of elements in this disclosure include active elements such as ICs, transistors, and diodes, and passive elements such as resistors, capacitors, and inductors. Other examples of elements include IC chips, LSI chips, and MEMS chips.

[0088] The element is mounted on a through-electrode substrate via a first junction. A junction commonly used for mounting elements can be used as the first junction. Examples of materials for the first junction include solder, gold or gold alloy, conductive paste, anisotropic conductive paste, and anisotropic conductive film.

[0089] Alternatively, an underfill resin portion may be provided by filling the space between the through-electrode substrate and the element. Furthermore, a molded resin portion may be provided by sealing the element with molded resin, thereby covering the element.

[0090] 3. Wiring board In this disclosure, a general-purpose wiring board can be used as the wiring board. From the viewpoint of cost, the substrate used for the wiring board is preferably a resin substrate. Examples of resin substrates include glass epoxy substrates and glass polyimide substrates.

[0091] The wiring board is electrically connected to the through-electrode substrate via a second joint. The material of the second joint is the same as that of the first joint.

[0092] 4.Applications The applications of the semiconductor device in this embodiment are not particularly limited and include, for example, notebook personal computers, tablet terminals, mobile phones, smartphones, digital video cameras, digital cameras, digital clocks, and servers.

[0093] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and achieves similar effects is included within the technical scope of this disclosure. [Examples]

[0094] (Example 1) A glass laminate as shown in Figure 1 was fabricated. A through-hole X with an hourglass-shaped cross-section was formed in a glass substrate 1 (thermal expansion coefficient 3.1 ppm / °C, thickness 400 μm). A titanium oxide layer 2, mainly composed of titanium oxide and containing chlorine atoms, was formed on the sidewall of the through-hole X by ALD (Advanced Laser Deposition). In the ALD method, TiCl4 was used as the metal halide and H2O as the oxidizing agent. By adjusting the supply time of the oxidizing agent, a titanium oxide (TiOx) layer containing chlorine atoms at the concentrations shown in Table 1 was formed. The chlorine atom content in the titanium oxide layer is the chlorine concentration at the center in the thickness direction of the titanium oxide layer, as measured by the dynamic secondary ion mass spectrometry (D-SIMS) method described above.

[0095] Next, a through-electrode layer 31 (conformal via) was formed on the surface of the metal oxide layer 2 formed on the side wall of the through-hole X. Copper (thermal expansion coefficient 16.5 ppm / °C) was used as the conductive material for the through-electrode layer.

[0096] (Examples 2 and 3) A glass laminate was manufactured in the same manner as in Example 1, except that the supply time of the oxidizing agent in the ALD method was adjusted so that the chlorine atom content in the titanium oxide layer was as shown in Table 1.

[0097] (Comparative example) A glass laminate was manufactured in the same manner as in Example 1, except that the supply time of the oxidizing agent in the ALD method was adjusted to be sufficiently long so that no chlorine atoms were included in the titanium oxide layer when forming the titanium oxide layer.

[0098] [evaluation] (Evaluation of cracks and copper wiring delamination) Using an optical microscope, the surfaces of the substrate and through-holes were observed to check for cracks in the substrate and the condition of delamination of the copper wiring.

[0099] (Resistivity measurement) The resistivity of the through-electrode layer of a glass laminate was measured. The resistivity was measured after 1000 cycles of treatment in a -55°C to +150°C environment, according to the JEDEC JESD22-A104 standard. A Digital MΩ Hitester (manufactured by HIOKI E.E. CORPORATION) was used as the resistivity measuring device. The terminals of the resistivity measuring device were placed in contact with pads pre-installed on the glass laminate, and the terminal voltage was set to a maximum of 5.5V for measurement.

[0100] [Table 1]

[0101] In Examples 1 to 3, where the titanium oxide layer contained chlorine atoms, no cracks or delamination of the copper wiring were observed. On the other hand, in the comparative example where the titanium oxide layer did not contain chlorine atoms (below the detection limit), cracks occurred. Furthermore, the chlorine atom content was 1 × 10⁻⁶. 17 atm / cm 3 The above 1 x 10 23 atm / cm 3 Examples 1 and 2, described below, were found to have lower resistivity compared to Example 3.

[0102] (Example of experiment) A glass laminate 10, as shown in Figure 7, was fabricated. Specifically, the glass laminate 10 was fabricated in the same manner as in Example 1, except that a glass substrate 1 with a straight cross-sectional shape for the through-hole X was used as the glass substrate 1. The thickness of the titanium oxide layer 2 at three locations (A-C) shown in Figure 7 was measured based on images of the cross-section of the glass laminate 10 taken using a scanning electron microscope (SEM). Each location was measured five times, and the arithmetic mean of the five thicknesses was adopted. The thickness of the titanium oxide layer 2 at location A was 15.2 nm, the thickness of the titanium oxide layer 2 at location B was 15.1 nm, and the thickness of the titanium oxide layer 2 at location C was 15.2 nm, confirming that the thickness of the titanium oxide layer 2 was almost constant regardless of the location.

[0103] This disclosure provides the following inventions. [1] Glass substrate and A metal oxide layer disposed on the surface of the glass substrate, The metal layer is disposed on the surface of the metal oxide layer opposite to the glass substrate, The above metal oxide layer is a glass laminate containing halogen atoms. [2] The above halogen atom is a chlorine atom, as described in [1], for the glass laminate. [3] The above metal oxide layer is a titanium oxide layer, as described in [1] or [2], a glass laminate. [4] The above glass substrate has through holes, The above metal oxide layer is arranged at least on the side wall of the through hole, The glass laminate according to any one of [1] to [3], wherein the metal layer includes a through electrode layer disposed on the surface of the metal oxide layer disposed on the side wall of the through hole. [5] The content of the halogen atoms in the metal oxide layer is 1 × 10 17 atm / cm 3 The above 1 x 10 23 atm / cm 3 A glass laminate as described in any of the following [1] to [4]. [6] A method for manufacturing a glass laminate according to any one of [1] to [5], A metal oxide layer formation step is performed on the surface of the glass substrate by atomic layer deposition, The process includes a metal layer formation step of forming the metal layer on the surface of the metal oxide layer opposite to the glass substrate, The above metal oxide layer formation step is, An adsorption treatment is performed by supplying a raw material gas containing a metal halide and adsorbing the metal halide onto the surface of the glass substrate. A first exhaust treatment process for exhausting the excess raw material gas, An oxidation treatment is performed by supplying an oxidizing agent and oxidizing the above metal halide, A method for manufacturing a glass laminate, comprising repeatedly performing a second exhaust treatment to exhaust excess oxidizing agent, with the above-mentioned metal oxide layer containing halogen atoms, as one cycle. [7] The method for producing a glass laminate according to [6], wherein the metal halide is TiCl4 and the metal oxide layer is a titanium oxide layer containing chlorine atoms. [8] In the above oxidation treatment, by adjusting the supply time of the oxidizing agent, The content of the halogen atoms in the metal oxide layer is 1 × 10 17 atm / cm 3 The above 1 x 10 23 atm / cm 3 A method for manufacturing a glass laminate according to [6] or [7], further adjusted as follows: [9] [4] A through electrode substrate comprising the glass laminate described above, An element is disposed on one side of the above-mentioned through-electrode substrate and electrically connected to the above-mentioned through-electrode layer, A semiconductor device comprising a wiring substrate disposed on the other side of the through-electrode substrate and electrically connected to the through-electrode layer. [Explanation of symbols]

[0104] 1 ... Glass substrate 2… Metal oxide layer 3 … Metal layer X … Through hole 10… Glass laminate 20… Through-electrode substrate 100... Semiconductor equipment

Claims

1. Glass substrate and A metal oxide layer disposed on the surface of the glass substrate, The metal layer is disposed on the surface of the metal oxide layer opposite to the glass substrate, The aforementioned metal oxide layer is a glass laminate containing halogen atoms.

2. The glass laminate according to claim 1, wherein the halogen atom is a chlorine atom.

3. The glass laminate according to claim 1, wherein the metal oxide layer is a titanium oxide layer.

4. The glass substrate has through holes, The metal oxide layer is arranged at least on the side wall of the through hole, The glass laminate according to claim 1, wherein the metal layer includes a through electrode layer disposed on the surface of the metal oxide layer disposed on the side wall of the through hole.

5. The content of the halogen atoms in the metal oxide layer is 1 × 10 １７ atm / cm ３ The above 1 x 10 ２３ atm / cm ３ The glass laminate according to claim 1, which is as follows:

6. A method for manufacturing a glass laminate according to any one of claims 1 to 5, A metal oxide layer formation step is performed on the surface of the glass substrate by atomic layer deposition, The process includes a metal layer forming step of forming the metal layer on the surface of the metal oxide layer opposite to the glass substrate, The metal oxide layer formation step is, An adsorption treatment is performed by supplying a raw material gas containing a metal halide and adsorbing the metal halide onto the surface of the glass substrate. A first exhaust treatment process for exhausting the excess raw material gas, An oxidation treatment is performed by supplying an oxidizing agent and oxidizing the metal halide, A method for manufacturing a glass laminate, comprising repeatedly performing a second exhaust treatment to exhaust excess oxidizing agent, with the process described above forming the metal oxide layer containing halogen atoms, as one cycle.

7. The aforementioned metal halide is TiCl ４ The method for manufacturing a glass laminate according to claim 6, wherein the metal oxide layer is a titanium oxide layer containing chlorine atoms.

8. In the oxidation treatment, by adjusting the supply time of the oxidizing agent, Adjust the content of the halogen atom in the metal oxide layer to be 1×10 １７ atm / cm ３ or more and 1×10 ２３ atm / cm ３ or less. The method for manufacturing a glass laminate according to claim 6.

9. A through-electrode substrate comprising the glass laminate described in claim 4, An element disposed on one side of the through-electrode substrate and electrically connected to the through-electrode layer, A semiconductor device comprising a wiring substrate disposed on the other side of the through-electrode substrate and electrically connected to the through-electrode layer.

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