CN111348617A - Substrate cleaning method and eutectic bonding method - Google Patents

Substrate cleaning method and eutectic bonding method Download PDF

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Publication number
CN111348617A
CN111348617A CN201811585113.7A CN201811585113A CN111348617A CN 111348617 A CN111348617 A CN 111348617A CN 201811585113 A CN201811585113 A CN 201811585113A CN 111348617 A CN111348617 A CN 111348617A
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China
Prior art keywords
substrate
pattern
germanium
eutectic bonding
tetramethylammonium hydroxide
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CN201811585113.7A
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Chinese (zh)
Inventor
李盈
丁刘胜
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Shanghai Industrial Utechnology Research Institute
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Shanghai Industrial Utechnology Research Institute
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Priority to CN201811585113.7A priority Critical patent/CN111348617A/en
Publication of CN111348617A publication Critical patent/CN111348617A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00222Integrating an electronic processing unit with a micromechanical structure
    • B81C1/00238Joining a substrate with an electronic processing unit and a substrate with a micromechanical structure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00841Cleaning during or after manufacture
    • B81C1/00849Cleaning during or after manufacture during manufacture

Abstract

The application provides a substrate cleaning method and a eutectic bonding method. The cleaning method of the substrate comprises the following steps: cleaning a first pattern formed on the surface of a substrate by using a solution of tetramethylammonium hydroxide (TMAH), wherein the material of the first pattern is germanium (Ge). According to the embodiment, germanium oxide on the surface of the germanium material pattern can be removed, so that the quality of eutectic bonding is improved, and the method is low in price and easy to implement.

Description

Substrate cleaning method and eutectic bonding method
Technical Field
The application relates to the technical field of semiconductors, in particular to a substrate cleaning method and a eutectic bonding method.
Background
In the manufacturing process of a semiconductor device, two substrates are often bonded to each other in order to realize miniaturization, multi-functionalization, and high performance of the device. In particular, in a micro-electro-mechanical system (MEMS) device having a movable microstructure, in order to prevent damage to the movable microstructure or maintain a stable pressure of an ambient gas to ensure stable functions of the device, it is often necessary to hermetically package the microstructure, and the hermeticity of the package requires stability for a long time. Such as MEMS acceleration sensors, gyroscopes, and pressure gauges, have high requirements for the hermeticity of the package. Such hermetic packaging is commonly achieved using substrate bonding techniques.
Among various substrate bonding techniques, eutectic bonding can achieve higher gas tightness and better gas tightness stability. Meanwhile, eutectic bonding often has the characteristics of lower bonding temperature and high bonding strength. For example, WO2006/101769 provides a technique for bonding and sealing a MEMS device to a CMOS substrate using AlGe eutectic bonding. The eutectic bonding of aluminum (Al) and germanium (Ge) provided by this technique is not only low in temperature (about 450 ℃), but the material is also CMOS compatible. Meanwhile, the AlGe eutectic also has better conductivity, so that the electric connection between the bonded substrates can be realized.
In the AlGe eutectic bonding, a single-layer film of Al or Ge or a multi-layer film of Al and Ge alternately stacked is generally formed on two substrates, the film is processed into a required pattern, then the two substrates are aligned and heated to a temperature slightly higher than the melting point of AlGe eutectic, wherein the temperature of the eutectic melting point is about 430 ℃, and the heating temperature is 430 ℃ for example. While heating, a certain pressure is applied between the two substrates to make the two substrates tightly contact. Although the substrate temperature is much lower than 938 ℃ pure Ge melting point or 660 ℃ pure Al melting point, Al and Ge will liquefy and interdiffuse at the interface between the two due to the temperature exceeding the eutectic melting point of AlGe. After interdiffusion, when the temperature is reduced to below the melting point of AlGe eutectic, Al and Ge form stable solid eutectic.
It should be noted that the above background description is only for the convenience of clear and complete description of the technical solutions of the present application and for the understanding of those skilled in the art. Such solutions are not considered to be known to the person skilled in the art merely because they have been set forth in the background section of the present application.
Disclosure of Invention
Germanium is stable at room temperature, but also forms germanium oxide films, such as GeO films, on the surface, and GeO gradually changes to GeO2A film; further, when water vapor is adsorbed on the surface of germanium, the passivation property of the oxide thin film is also deteriorated, and a thick oxide film is formed. The melting point of the germanium oxide is (1115 +/-4) DEG C, which is higher than the melting point 938 ℃ of pure Ge, if the oxide generated on the surface of the Ge is excessive, the eutectic melting point is affected, the bonding quality of the region with the germanium oxide is reduced, and the bonding uniformity is affected.
The reaction equation for the germanium oxidation process is as follows:
(1) the germanium is oxidized to GeO: 2Ge + O2 ═ 2GeO
(2) GeO was oxidized to GeO 2: 2GeO + O2 ═ 2GeO2
The embodiment of the application provides a substrate cleaning method and a eutectic bonding method, wherein a germanium material pattern on the surface of a substrate is cleaned by using a tetramethylammonium hydroxide (TMAH) solution, so that germanium oxide on the surface of the germanium material pattern can be removed, the quality of eutectic bonding is improved, and the method is low in price and easy to implement.
According to an aspect of an embodiment of the present application, there is provided a method for cleaning a substrate, including:
cleaning a first pattern formed on the surface of a substrate by using a solution of tetramethylammonium hydroxide (TMAH), wherein the material of the first pattern is germanium (Ge).
According to another aspect of an embodiment of the present application, wherein the solution of tetramethylammonium hydroxide (TMAH) is a developer of photoresist.
According to another aspect of the embodiments of the present application, wherein the mass percentage of the tetramethylammonium hydroxide (TMAH) in the solution of the tetramethylammonium hydroxide is 2% to 4%.
According to another aspect of an embodiment of the present application, there is provided a eutectic bonding method including:
cleaning a first pattern formed on the surface of a first substrate by using a solution of tetramethylammonium hydroxide (TMAH), wherein the material of the first pattern is germanium (Ge); and
and the first pattern formed on the surface of the first substrate and the second pattern formed on the surface of the second substrate are opposite and contacted, and pressure and temperature are applied to the first substrate and the second substrate, so that the first substrate and the second substrate are subjected to eutectic bonding through the first pattern and the second pattern, wherein the material of the second pattern is different from that of the first pattern.
According to another aspect of the embodiment of the present application, wherein the material of the second pattern is aluminum (Al).
The beneficial effect of this application lies in: the germanium material pattern on the surface of the substrate is cleaned by using a tetramethylammonium hydroxide (TMAH) solution, so that germanium oxide on the surface of the germanium material pattern can be removed, the quality of eutectic bonding is improved, and the method is low in price and easy to implement.
Specific embodiments of the present application are disclosed in detail with reference to the following description and drawings, indicating the manner in which the principles of the application may be employed. It should be understood that the embodiments of the present application are not so limited in scope. The embodiments of the application include many variations, modifications and equivalents within the spirit and scope of the appended claims.
Features that are described and/or illustrated with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments, in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used herein, is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps or components.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the application, are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. It is obvious that the drawings in the following description are only some embodiments of the application, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. In the drawings:
FIG. 1 is a schematic view of a eutectic bonding method according to embodiment 1 of the present application;
fig. 2 is a schematic view of a bonding interface after bonding according to the bonding method of the present embodiment after being scanned by an ultrasonic scanner;
fig. 3 is a schematic view of a bonded interface being scanned by an ultrasonic scanner after bonding a first substrate and a second substrate directly without the process of step 101.
Detailed Description
The foregoing and other features of the present application will become apparent from the following description, taken in conjunction with the accompanying drawings. In the description and drawings, particular embodiments of the application are disclosed in detail as being indicative of some of the embodiments in which the principles of the application may be employed, it being understood that the application is not limited to the described embodiments, but, on the contrary, is intended to cover all modifications, variations, and equivalents falling within the scope of the appended claims.
In the description of the embodiments of the present application, a direction parallel to the surface of the substrate is referred to as "lateral direction" and a direction perpendicular to the surface of the substrate is referred to as "longitudinal direction" for convenience of description, wherein the "thickness" of each component means a dimension of the component in the "longitudinal direction".
Example 1
The embodiment of the application provides a eutectic bonding method. Fig. 1 is a schematic view of the eutectic bonding method, and as shown in fig. 1, the eutectic bonding method includes:
step 101, cleaning a first pattern formed on a surface of a first substrate by using a tetramethylammonium hydroxide (TMAH) solution, wherein a material of the first pattern is germanium (Ge); and
and 102, oppositely arranging and contacting the first pattern formed on the surface of the first substrate and the second pattern formed on the surface of the second substrate, and applying pressure and temperature to the first substrate and the second substrate to enable the first substrate and the second substrate to be subjected to eutectic bonding through the first pattern and the second pattern, wherein the material of the second pattern is different from that of the first pattern.
In step 101 of this embodiment, the first pattern formed on the surface of the first substrate is cleaned by using a solution of tetramethylammonium hydroxide (TMAH), for example, the first pattern formed on the surface of the first substrate is rinsed by using the solution of tetramethylammonium hydroxide (TMAH), and then spin-drying or nitrogen blow-drying is performed.
In step 101 of this embodiment, when a base is present in a solution of tetramethylammonium hydroxide (TMAH), the germanium oxide on the surface of the first pattern can interact with the base to form germanate, so that the germanium oxide on the surface of the first pattern is converted into germanate and removed.
The reaction equation of the germanate generated by the interaction of the germanium oxide and the alkali is as follows:
GeO2+2OH-=GeO3 2-+H2O
in this embodiment, the solution of tetramethylammonium hydroxide (TMAH) may be a developer of photoresist. In one embodiment, the photoresist developer solution has a tetramethylammonium hydroxide content of 2% to 4% by weight, for example, a tetramethylammonium hydroxide content of 2.38% by weight.
In this embodiment, the photoresist developer solution containing tetramethylammonium hydroxide (TMAH) is relatively low cost and can be used to perform a single-wafer cleaning of the first substrate, thereby enabling a relatively low cost cleaning of the first pattern of germanium material on the surface of the first substrate.
In contrast, if the first pattern of the germanium material on the first substrate surface is cleaned with another solution, for example, a 1# cleaning solution commonly used in the semiconductor manufacturing process (for example, the 1# cleaning solution is a mixture of ammonia, hydrogen peroxide and water, i.e., NH)4OH:H2O2:H2O ═ 1:1:5 to 1:1:7), which is expensive and can only be mass produced.
In this embodiment, in step 101, the first pattern formed on the surface of the first substrate can be cleaned to remove the oxide on the surface of the first pattern, so as to provide a pure surface of germanium material for eutectic bonding in step 102.
In this embodiment, the first substrate cleaned in step 101 may be applied to other fields besides eutectic bonding.
In step 102 of this embodiment, the first pattern of the germanium material on the cleaned surface of the first substrate and the second pattern formed on the surface of the second substrate are opposed to each other and contacted, and pressure and temperature are applied to the first substrate and the second substrate, so that the first substrate and the second substrate are eutectic bonded through the first pattern and the second pattern.
In this embodiment, the material of the second pattern is different from the material of the first pattern, whereby a eutectic is formed between the first pattern and the second pattern, so that a eutectic bond is formed between the first substrate and the second substrate.
In one embodiment, the material of the second pattern of the second substrate surface is aluminum (Al), whereby the first substrate and the second substrate form a eutectic bond of aluminum (Al) and germanium (Ge). In addition, the present embodiment may not be limited thereto, and the material of the second pattern may also be other material different from germanium.
In this embodiment, the bond quality in step 102 is higher because the first pattern of germanium material of the first substrate is cleaned in step 101.
Fig. 2 is a schematic view of a bonded interface after being bonded by the bonding method according to the present embodiment, and fig. 3 is a schematic view of a bonded interface after being directly bonded to a first substrate and a second substrate without being subjected to the process of step 101, being scanned by an ultrasonic scanner.
As shown in fig. 2, after bonding according to the bonding method of the present embodiment, the bonding interface of Al-Ge eutectic bonding is uniform, and the bonding quality is high. In contrast, as shown in fig. 3, after the first substrate and the second substrate are directly bonded without the process of step 101, the bonding interface of the Al-Ge eutectic bonding is not uniform, where the region 1 is a region with better Al-Ge eutectic bonding quality, and the region 2 is a region with poorer bonding quality.
According to the embodiment, the germanium material pattern on the surface of the substrate is cleaned by using a tetramethylammonium hydroxide (TMAH) solution, so that germanium oxide on the surface of the germanium material pattern can be removed, the quality of eutectic bonding can be improved, and the method is cheap and easy to implement.
The present application has been described in conjunction with specific embodiments, but it should be understood by those skilled in the art that these descriptions are intended to be illustrative, and not limiting. Various modifications and adaptations of the present application may occur to those skilled in the art based on the spirit and principles of the application and are within the scope of the application.

Claims (7)

1. A method of cleaning a substrate comprising:
cleaning a first pattern formed on the surface of a substrate by using a solution of tetramethylammonium hydroxide (TMAH), wherein the material of the first pattern is germanium (Ge).
2. The method for cleaning a substrate according to claim 1,
the solution of tetramethylammonium hydroxide (TMAH) is a developing solution of photoresist.
3. The method for cleaning a substrate according to claim 1 or 2,
in the solution of tetramethylammonium hydroxide (TMAH), the mass percent of the tetramethylammonium hydroxide is 2-4%.
4. A eutectic bonding method, comprising:
cleaning a first pattern formed on the surface of a first substrate by using a solution of tetramethylammonium hydroxide (TMAH), wherein the material of the first pattern is germanium (Ge); and
and the first pattern formed on the surface of the first substrate and the second pattern formed on the surface of the second substrate are opposite and contacted, and pressure and temperature are applied to the first substrate and the second substrate, so that the first substrate and the second substrate are subjected to eutectic bonding through the first pattern and the second pattern, wherein the material of the second pattern is different from that of the first pattern.
5. The eutectic bonding method of claim 4,
the material of the second pattern is aluminum (Al).
6. The eutectic bonding method of claim 4,
the solution of tetramethylammonium hydroxide (TMAH) is a developing solution of photoresist.
7. The eutectic bonding method according to any one of claims 4 to 6,
in the solution of tetramethylammonium hydroxide (TMAH), the mass percent of the tetramethylammonium hydroxide is 2-4%.
CN201811585113.7A 2018-12-24 2018-12-24 Substrate cleaning method and eutectic bonding method Pending CN111348617A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5935871A (en) * 1997-08-22 1999-08-10 Motorola, Inc. Process for forming a semiconductor device
US20050040442A1 (en) * 2003-08-21 2005-02-24 Andreas Michael T. Wafer cleaning method and resulting wafer
US20050239672A1 (en) * 2004-04-14 2005-10-27 Samsung Electronics Co., Ltd. Cleaning solution of silicon germanium layer and cleaning method using the same
CN101171665A (en) * 2005-03-18 2008-04-30 因文森斯公司 Method of fabrication of AI/GE bonding in a wafer packaging environment and a product produced therefrom
CN103594411A (en) * 2012-08-13 2014-02-19 中芯国际集成电路制造(上海)有限公司 Formation method of silicon germanium on insulator
US20150031189A1 (en) * 2013-07-24 2015-01-29 Taiwan Semiconductor Manufacturing Co., Ltd. Mechanisms for cleaning substrate surface for hybrid bonding
TW201600183A (en) * 2014-06-16 2016-01-01 Kurita Water Ind Ltd Clean method, clean water supply device and clean device for element Ge substrate
CN106847717A (en) * 2015-12-04 2017-06-13 上海新微技术研发中心有限公司 Eutectic bonding method and semiconductor device
CN108100986A (en) * 2016-11-24 2018-06-01 上海新微技术研发中心有限公司 Eutectic bonding method and semiconductor device

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5935871A (en) * 1997-08-22 1999-08-10 Motorola, Inc. Process for forming a semiconductor device
US20050040442A1 (en) * 2003-08-21 2005-02-24 Andreas Michael T. Wafer cleaning method and resulting wafer
US20050239672A1 (en) * 2004-04-14 2005-10-27 Samsung Electronics Co., Ltd. Cleaning solution of silicon germanium layer and cleaning method using the same
CN101171665A (en) * 2005-03-18 2008-04-30 因文森斯公司 Method of fabrication of AI/GE bonding in a wafer packaging environment and a product produced therefrom
CN103594411A (en) * 2012-08-13 2014-02-19 中芯国际集成电路制造(上海)有限公司 Formation method of silicon germanium on insulator
US20150031189A1 (en) * 2013-07-24 2015-01-29 Taiwan Semiconductor Manufacturing Co., Ltd. Mechanisms for cleaning substrate surface for hybrid bonding
TW201600183A (en) * 2014-06-16 2016-01-01 Kurita Water Ind Ltd Clean method, clean water supply device and clean device for element Ge substrate
CN106847717A (en) * 2015-12-04 2017-06-13 上海新微技术研发中心有限公司 Eutectic bonding method and semiconductor device
CN108100986A (en) * 2016-11-24 2018-06-01 上海新微技术研发中心有限公司 Eutectic bonding method and semiconductor device

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Application publication date: 20200630