CN102070120B - Preparation method for high-density interposer for microelectronic system-in-package - Google Patents
Preparation method for high-density interposer for microelectronic system-in-packageDownload PDFInfo
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Abstract
Translated fromChineseDescription
Translated fromChinese技术领域technical field
本发明涉及一种微电子制造技术，尤其涉及一种用于微电子系统级封装的高密度转接板的制备方法。 The invention relates to a microelectronic manufacturing technology, in particular to a preparation method of a high-density adapter plate used for microelectronic system level packaging. the
背景技术Background technique
微电子系统中，芯片上线宽通常是几十个纳米，而PCB板上通常是几十个至几百个微米。通常利用各种转接板(该转接板即英文中的interposer，包括基板)将芯片与PCB板互连，实现纳米至微米尺度的过渡。对转接板的要求有很多，例如要求有较低的热膨胀系数，高的密度，高刚度和低的介电常数等。 In microelectronic systems, the line width on the chip is usually tens of nanometers, while that on the PCB is usually tens to hundreds of microns. Usually, various adapter boards (the interposer in English, including the substrate) are used to interconnect the chip and the PCB board to realize the transition from nanometer to micrometer scale. There are many requirements for the adapter plate, such as low thermal expansion coefficient, high density, high stiffness and low dielectric constant. the
现有的有机材料转接板的问题在于其热膨胀系数较高，与芯片的热失配较大，而且其模量较低，使基板的翘曲度较高，因此难以实现高密度互连。 The problem with the existing organic material interposer is that it has a high thermal expansion coefficient, a large thermal mismatch with the chip, and its low modulus, which makes the substrate warpage high, so it is difficult to achieve high-density interconnection. the
现有的硅通孔(TSV)工艺是目前发展的主要方向，它首先是在硅上采用干法(DRIE)或者激光加工等方法制作尺度较小的通孔，然后再采用电镀的方法将孔金属化，但是效率较低，成本较高；目前采用将硅片减薄至50微米以下甚至更薄，大大降低了成本，但是整个过程需要几十个小时，可靠性也难以满足工业界的要求。 The existing through-silicon via (TSV) process is the main direction of development at present. It first uses dry method (DRIE) or laser processing to make small-scale through-holes on silicon, and then uses electroplating to seal the holes. Metallization, but the efficiency is low and the cost is high; currently, the silicon wafer is thinned to less than 50 microns or even thinner, which greatly reduces the cost, but the whole process takes dozens of hours, and the reliability is difficult to meet the requirements of the industry . the
采用玻璃作为转接板正成为关注的方向。在玻璃上加工通孔是一个难题。采用DRIE的方法利用气体对玻璃进行刻蚀，刻蚀速率仅为750nm/min，不仅所刻的结构形状和尺寸局限性大，无法实现大高宽比，而且加工效率低，成本高。目前主要采用激光加工的方法来制备通孔，但是激光加工的成本较高，而且加工的孔形状也不规则，加工3-10微米的小孔时，其速度更慢，加工以后仍然需要采用电化学方法进行金属化，在要求高密度、小尺寸引线互连时，效率较低，成本较高。 The use of glass as the interposer is becoming the direction of attention. Machining vias in glass is a challenge. The DRIE method uses gas to etch the glass, and the etching rate is only 750nm/min. Not only the shape and size of the etched structure are limited, and a large aspect ratio cannot be achieved, but also the processing efficiency is low and the cost is high. At present, laser processing is mainly used to prepare through holes, but the cost of laser processing is high, and the shape of the processed holes is irregular. When processing small holes of 3-10 microns, the speed is slower. Metallization by chemical methods is less efficient and more costly when high-density, small-size lead interconnects are required. the
因此，目前急需发展一种低成本、高效率、高密度的转接板。 Therefore, there is an urgent need to develop a low-cost, high-efficiency, and high-density interposer board. the
发明内容Contents of the invention
本发明主要提供一种低成本、高效率的用于微电子系统级封装的高密度转接板的制备方法。 The invention mainly provides a low-cost, high-efficiency method for preparing a high-density adapter plate used for microelectronic system level packaging. the
本发明采用如下技术方案： The present invention adopts following technical scheme:
一种用于微电子系统级封装的高密度转接板的制备方法，包括以下步骤：A method for preparing a high-density adapter board for microelectronic system-in-package, comprising the following steps:
第一步，制备定向生长的碳纳米管束阵列2，碳纳米管束的直径为0.5-30微米，间距为0.8-100微米，长度为40-500微米；The first step is to prepare an array 2 of oriented carbon nanotube bundles, the carbon nanotube bundles have a diameter of 0.5-30 microns, a spacing of 0.8-100 microns, and a length of 40-500 microns;
第二步，在上述的定向生长碳纳米管束表面沉积金属钨1形成导体阵列；In the second step, metal tungsten 1 is deposited on the surface of the above-mentioned directional growth carbon nanotube bundle to form a conductor array;
第三步，使得硼硅玻璃与导体阵列在硼硅玻璃熔融状态下形成复合体，The third step is to make the borosilicate glass and the conductor array form a complex in the molten state of the borosilicate glass,
第四步，对于形成的复合体的上下表面进行磨抛使得沉积金属钨的碳纳米管束端部暴露，从而得到用于系统级封装的高密度转接板。The fourth step is to grind and polish the upper and lower surfaces of the formed complex so that the ends of the carbon nanotube bundles deposited with metal tungsten are exposed, so as to obtain a high-density adapter plate for system-in-level packaging.
上述技术方案中，第三步采用负压法使得导体阵列与玻璃形成复合体，具体步骤为：首先将上述所述的金属阵列转移到预先准备的硅腔中，并将硼硅玻璃与硅在真空中进行阳极键合，使得硅腔密封；再将上述键合好的两圆片在一个大气压下加热到玻璃的软化温度以上，熔融玻璃在负压的作用下进入硅腔与所述碳纳米管束阵列形成复合体，冷却，退火。通过等离子增强化学气相沉积的方法合成所述的碳纳米管束阵列。碳纳米管束表面沉积金属钨的厚度为0.5-2微米。在碳纳米管束表面沉积金属钨的方法为电子束蒸发的方式。所述硼硅玻璃为Pyrex7740玻璃，所述第四步的加热温度为850℃-900℃。所述硼硅玻璃为BOROFLOAT33玻璃。所述第五步的磨抛方法为化学机械腐蚀。 In the above technical solution, the third step adopts the negative pressure method to make the conductor array and the glass form a composite body. The specific steps are: first, transfer the above-mentioned metal array to the pre-prepared silicon cavity, and place the borosilicate glass and silicon in the Anodic bonding is carried out in vacuum to seal the silicon cavity; then the above-mentioned bonded wafers are heated above the softening temperature of the glass at an atmospheric pressure, and the molten glass enters the silicon cavity and the carbon nanometers under negative pressure. The array of tube bundles is formed into a composite body, cooled, and annealed. The carbon nanotube bundle array is synthesized by a plasma-enhanced chemical vapor deposition method. The thickness of metal tungsten deposited on the surface of the carbon nanotube bundle is 0.5-2 microns. The method for depositing metal tungsten on the surface of the carbon nanotube bundle is the way of electron beam evaporation. The borosilicate glass is Pyrex7740 glass, and the heating temperature in the fourth step is 850°C-900°C. The borosilicate glass is BOROFLOAT33 glass. The grinding and polishing method in the fifth step is chemical mechanical corrosion. the
本发明获得如下效果： The present invention obtains following effect:
1. 本发明采用定向生长的碳纳米管束阵列作为模板，采用钨作为导电金属和浸润金属，制备了玻璃转接板，其中碳纳米管阵列与钨的复合体作为导体材料。由于本发明采用定向生长的碳纳米管束阵列，因此可制备高密度的通孔互连线。现有碳纳米管束可实现微米至亚微米直径，线宽为微米至亚微米，长度为亚微米至几毫米的制造，因此采用玻璃与定向生长的碳纳米管束的复合可望实现高密度的互连，导体直径、线宽、长度精确可调，可实现几十微米至亚微米直径，线宽为几百微米至亚微米，长度为亚微米至几毫米范围的制造。本发明采用钨金属与硼硅玻璃具有优异的润湿性，因此很容易复合；此外，钨与碳纳米管阵列粘结性好，能够促进玻璃与钨的复合程度，从而提高复合体的可靠性；钨金属(约百万分之5)及碳纳米管具有较低的热膨胀系数，热稳定性好，因此制备得到的复合体在承受较高的热循环载荷时，具有较高的可靠性；钨的导电性较好，碳纳米管束也具有较高的导电性，钨与碳纳米管束的复合体也具有较好的导电性，而且能够实现电互连功能；此外，钨与碳纳米管束的复合体在端部很容易与其它金属，例如铜、锡合金等形成良好的键合，形成的焊盘连接点具有较高的可靠性，这是单一采用碳纳米管互连所不具备的。1. The present invention adopts the directional growth carbon nanotube bundle array as a template, uses tungsten as the conductive metal and the infiltrating metal, and prepares a glass adapter plate, wherein the composite of the carbon nanotube array and tungsten is used as the conductor material. Since the invention adopts the array of carbon nanotube bundles grown in an orientation, high-density through-hole interconnection lines can be prepared. Existing carbon nanotube bundles can achieve micron to submicron diameter, micron to submicron line width, and submicron to several millimeters in length. Therefore, the combination of glass and oriented carbon nanotube bundles is expected to achieve high-density interconnection The conductor diameter, line width, and length can be precisely adjusted, and can be manufactured in the range of tens of microns to sub-micron in diameter, hundreds of microns to sub-micron in line width, and sub-micron to several millimeters in length. In the present invention, tungsten metal and borosilicate glass have excellent wettability, so they are easy to compound; in addition, tungsten and carbon nanotube arrays have good adhesion, which can promote the degree of compounding of glass and tungsten, thereby improving the reliability of the compound ; Tungsten metal (about 5 parts per million) and carbon nanotubes have a low coefficient of thermal expansion and good thermal stability, so the prepared composite has high reliability when subjected to high thermal cycle loads; Tungsten has good conductivity, carbon nanotube bundles also have high conductivity, and the composite of tungsten and carbon nanotube bundles also has good conductivity, and can realize the function of electrical interconnection; in addition, the combination of tungsten and carbon nanotube bundles The composite body is easy to form good bonding with other metals at the end, such as copper, tin alloy, etc., and the formed pad connection point has high reliability, which is not available in the single interconnection of carbon nanotubes.
2. 硼硅玻璃(包括BOROFLOAT33，Pyrex7740-美国康宁公司生产)能润湿钨表面。它具有着高透光率、较高的强度、高模量和低介电常数等特点，使得转接板具有良好的光、电、机械性能，并具有较高的可靠性。此外，由于碳纳米管阵列与钨形成的复合导体表面粗糙度比较低(几纳米至几十纳米)，因此制备的导的玻璃转接板尤其适用于高频应用。由于碳纳米管束、硼硅玻璃以及钨均可承受高温，因此该玻璃转接板也适合于高温应用。 2. Borosilicate glass (including BOROFLOAT33, Pyrex7740-produced by Corning, USA) can wet the surface of tungsten. It has the characteristics of high light transmittance, high strength, high modulus and low dielectric constant, so that the adapter board has good optical, electrical and mechanical properties, and has high reliability. In addition, because the surface roughness of the composite conductor formed by the carbon nanotube array and tungsten is relatively low (several nanometers to tens of nanometers), the prepared conductive glass interposer is especially suitable for high-frequency applications. Since carbon nanotube bundles, borosilicate glass, and tungsten can withstand high temperatures, the glass interposer is also suitable for high-temperature applications. the
3. 本发明中是将玻璃熔融直接浇铸到金属阵列中，制备速度快，效率高，大大降低了成本；由于定向生长碳纳米管阵列已经可以进行圆片级制造(采用品牌为Blackmagic气相沉积设备制造)，本发明还可以制备圆片级的玻璃转接板，因此制备的成本能够得到进一步降低。 3. In the present invention, the molten glass is directly cast into the metal array, the preparation speed is fast, the efficiency is high, and the cost is greatly reduced; because the array of directional growth carbon nanotubes can already be manufactured at the wafer level (using a brand of Blackmagic vapor deposition equipment manufacturing), the present invention can also prepare a wafer-level glass interposer, so the manufacturing cost can be further reduced. the
4. 本发明中的玻璃的模量比硅的模量高，而且加工过程中不需要将玻璃基片减薄，因此玻璃基板的防翘曲的能力比硅好基板。 4. The modulus of the glass in the present invention is higher than that of silicon, and there is no need to thin the glass substrate during processing, so the ability of the glass substrate to prevent warping is better than that of the silicon substrate. the
5. 本发明中使用的玻璃的介电常数比硅的低，因此较硅基板减少了电容耦合和信号串扰。本发明中的硅腔与玻璃的阳极键合具有很高的强度，密闭性好的特点，在加热过程中不易发生泄漏而导致玻璃在与金属阵列结合的过程中产生气泡。在温度400°C，电压直流600V的键合条件下，阳极键合能够达到最好的密封效果。 5. The dielectric constant of the glass used in the present invention is lower than that of silicon, thus reducing capacitive coupling and signal crosstalk compared to silicon substrates. The anodic bonding of the silicon cavity and the glass in the present invention has the characteristics of high strength and good airtightness, and it is not easy to leak during the heating process, which will cause bubbles to be generated in the process of combining the glass with the metal array. Under the bonding conditions of temperature 400°C and voltage DC 600V, anodic bonding can achieve the best sealing effect. the
6. 本发明中采用的退火工艺可以有效的消除玻璃承受高温与金属阵列结合过程中形成的应力，从而使其强度韧性更高。退火温度为550℃～570℃范围内，保温时间为30min，然后缓慢冷却到室温。在该条件下退火，能有效退去应力，而过低的退火温度则无法有效去除玻璃内部应力。 6. The annealing process adopted in the present invention can effectively eliminate the stress formed when the glass is subjected to high temperature and combined with the metal array, so that its strength and toughness are higher. The annealing temperature is within the range of 550°C to 570°C, the holding time is 30min, and then slowly cooled to room temperature. Annealing under this condition can effectively relieve the stress, but too low annealing temperature cannot effectively remove the internal stress of the glass. the
7. 本发明中可采用浓度为25%的TMAH溶液去除生长碳纳米管的硅，这样可以有效地去除硅片而不腐蚀玻璃，选择硅片、玻璃比为1000:1。 7. In the present invention, the TMAH solution with a concentration of 25% can be used to remove the silicon for growing carbon nanotubes, so that the silicon wafer can be effectively removed without corroding the glass, and the silicon wafer and glass ratio are selected to be 1000:1. the
本发明具有金属通孔密度高，导热性好，制备周期短的特点，也可以广泛应用于MEMS制造中的玻璃基板的制备。 The invention has the characteristics of high metal through-hole density, good thermal conductivity and short preparation cycle, and can also be widely used in the preparation of glass substrates in MEMS manufacturing. the
附图说明Description of drawings
图1为碳纳米管束阵列的截面示意图。 FIG. 1 is a schematic cross-sectional view of a carbon nanotube bundle array. the
图2为碳纳米管束阵列金属化后的截面示意图。 Fig. 2 is a schematic cross-sectional view of a carbon nanotube bundle array after metallization. the
图3为固体金属通孔的玻璃基板示意图。 Figure 3 is a schematic diagram of a glass substrate with solid metal vias. the
图4为上下磨抛后露出固体金属通孔(中心为碳管)端面的玻璃转接板截面示意图。4 is a schematic cross-sectional view of a glass adapter plate exposed to the end face of a solid metal through hole (with a carbon tube in the center) after upper and lower grinding and polishing.
图5为固体金属通孔的玻璃基板俯视示意图。5 is a schematic top view of a glass substrate with solid metal vias.
具体实施方式Detailed ways
实施例1Example 1
一种用于微电子系统级封装的高密度转接板的制备方法，包括以下步骤：A method for preparing a high-density adapter board for microelectronic system-in-package, comprising the following steps:
第一步，制备定向生长的碳纳米管束阵列2，碳纳米管束的直径为0.5-30微米，例如为0.8微米，2微米，3微米，5微米，10微米，20微米，间距为0.8-100微米，例如为1微米，3微米，5微米，8微米，10微米，20微米，30微米，50微米，80微米，长度为40-500微米，例如可以为45微米，60微米，100微米，200微米，300微米，400微米；The first step is to prepare an array 2 of oriented carbon nanotube bundles, the diameter of the carbon nanotube bundles is 0.5-30 microns, such as 0.8 microns, 2 microns, 3 microns, 5 microns, 10 microns, 20 microns, and the spacing is 0.8-100 microns Micron, such as 1 micron, 3 micron, 5 micron, 8 micron, 10 micron, 20 micron, 30 micron, 50 micron, 80 micron, the length is 40-500 micron, such as 45 micron, 60 micron, 100 micron, 200 microns, 300 microns, 400 microns;
第二步，在上述的定向生长碳纳米管束表面沉积金属钨1形成导体阵列；钨的厚度为0.1-20微米，例如可以为0.2微米，0.8微米，1微米，5微米，10微米，15微米。In the second step, metal tungsten 1 is deposited on the surface of the above-mentioned directional growth carbon nanotube bundle to form a conductor array; the thickness of tungsten is 0.1-20 microns, for example, it can be 0.2 microns, 0.8 microns, 1 micron, 5 microns, 10 microns, 15 microns .
第三步，使得硼硅玻璃与导体阵列在硼硅玻璃熔融状态下形成复合体， The third step is to make the borosilicate glass and the conductor array form a complex in the molten state of the borosilicate glass,
第四步，对于形成的复合体的上下表面进行磨抛使得沉积金属钨的碳纳米管束端部暴露，从而得到用于系统级封装的高密度转接板。The fourth step is to grind and polish the upper and lower surfaces of the formed complex so that the ends of the carbon nanotube bundles deposited with metal tungsten are exposed, so as to obtain a high-density adapter plate for system-in-level packaging.
上述技术方案中，第三步可以采用正的压力驱动将玻璃渗入导体阵列之间，也可以采用负压力抽吸熔融玻璃形成玻璃与导体阵列的复合体，再将玻璃冷却，退火。本发明可通过等离子增强化学气相沉积的方法合成所述的碳纳米管束阵列。在碳纳米管束表面沉积金属钨的方法为电子束蒸发的方式。所述硼硅玻璃为Pyrex7740玻璃，对应的所述加热熔化温度为850℃-900℃，例如860℃，880℃。所述硼硅玻璃也可以BOROFLOAT33玻璃。所述第五步的磨抛方法为化学机械腐蚀。 In the above technical solution, the third step can be driven by positive pressure to infiltrate the glass between the conductor arrays, or negative pressure can be used to suck the molten glass to form a composite of glass and conductor arrays, and then the glass is cooled and annealed. In the present invention, the carbon nanotube bundle array can be synthesized by the method of plasma enhanced chemical vapor deposition. The method for depositing metal tungsten on the surface of the carbon nanotube bundle is the way of electron beam evaporation. The borosilicate glass is Pyrex7740 glass, and the corresponding heating melting temperature is 850°C-900°C, such as 860°C, 880°C. The borosilicate glass can also be BOROFLOAT33 glass. The grinding and polishing method in the fifth step is chemical mechanical corrosion. the
实施例2Example 2
一种用于微电子系统级封装的高密度转接板的制备方法，包括以下步骤：A method for preparing a high-density adapter board for microelectronic system-in-package, comprising the following steps:
第一步，制备定向生长的碳纳米管束阵列，碳纳米管束的直径为3微米，间距为5微米，长度为200微米；生长方法是等离子增强气相沉积方法等，The first step is to prepare a directional growth carbon nanotube bundle array, the carbon nanotube bundle has a diameter of 3 microns, a spacing of 5 microns, and a length of 200 microns; the growth method is a plasma-enhanced vapor deposition method, etc.,
第二步，在上述所述的碳纳米管束表面沉积金属钨；可以在碳纳米管表面制备一层钨，钨的厚度为3微米，制备的方法可以是溅射或者电子束蒸发或者电镀等方法，电子束蒸发(Ebeam)能使碳纳米管阵列的表面覆盖厚度均匀的钨，且具有较低的表面粗糙度。The second step is to deposit metal tungsten on the surface of the above-mentioned carbon nanotube bundle; a layer of tungsten can be prepared on the surface of the carbon nanotube, and the thickness of tungsten is 3 microns. The preparation method can be sputtering, electron beam evaporation or electroplating. , Electron beam evaporation (Ebeam) can make the surface of the carbon nanotube array covered with uniform thickness of tungsten, and has a low surface roughness.
第三步，将上述的金属化后的碳纳米管束转移到预先准备的硅腔中，并将Pyrex7740玻璃与硅在真空中进行阳极键合，使得硅腔密封；真空度小于1Pa，例如0.1Pa，0.01Pa，阳极键合；工艺条件为：温度400℃，电压：600V。 The third step is to transfer the above-mentioned metallized carbon nanotube bundles into the pre-prepared silicon cavity, and anodically bond the Pyrex7740 glass and silicon in vacuum, so that the silicon cavity is sealed; the vacuum degree is less than 1Pa, such as 0.1Pa , 0.01Pa, anode bonding; process conditions: temperature 400 ° C, voltage: 600V. the
第四步，将上述键合好的两圆片在一个大气压下加热到850℃-900℃下，玻璃在腔内负压的作用下进入硅腔，并与所述金属化后的碳纳米管束复合，冷却，退火， The fourth step is to heat the above-mentioned two bonded wafers to 850°C-900°C under an atmospheric pressure, and the glass enters the silicon cavity under the action of negative pressure in the cavity, and combines with the metallized carbon nanotube bundles compounding, cooling, annealing,
第五步，对于形成的复合体的上下表面进行磨抛使得沉积金属钨的碳纳米管束端部暴露，从而得到用于系统级封装的高密度转接板，在将沉积金属钨的碳纳米管束端部暴露后，可在其表面制作用于引线互连的金属焊盘，由于钨的存在，钨与金属形成的焊点的可靠性较高，从而克服了现有碳纳米管与金属的电连接可靠性差的缺点。The fifth step is to grind and polish the upper and lower surfaces of the formed composite so that the ends of the carbon nanotube bundles deposited with metal tungsten are exposed, so as to obtain a high-density adapter board for system-level packaging, and the carbon nanotube bundles that will deposit metal tungsten After the end is exposed, a metal pad for lead interconnection can be made on its surface. Due to the existence of tungsten, the reliability of the solder joint formed by tungsten and metal is high, thus overcoming the current electrical gap between carbon nanotubes and metal. The disadvantage of poor connection reliability.
上述技术方案中，通过等离子增强化学气相沉积的方法合成所述的碳纳米管束阵列，碳纳米管束表面沉积金属钨的厚度为0.5-2微米，在碳纳米管束表面沉积金属钨的方法为电子束蒸发的方式，所述第五步的磨抛方法为化学机械腐蚀。 In the above technical scheme, the carbon nanotube bundle array is synthesized by plasma-enhanced chemical vapor deposition, the thickness of metal tungsten deposited on the surface of the carbon nanotube bundle is 0.5-2 microns, and the method of depositing metal tungsten on the surface of the carbon nanotube bundle is electron beam In the way of evaporation, the grinding and polishing method in the fifth step is chemical mechanical corrosion. the
实施例3Example 3
一种用于微电子系统级封装的高密度转接板的制备方法，包括以下步骤：第一步，采用在硅圆片上生长碳纳米管束阵列；第二步，对上述所述的碳纳米管束阵列金属化；第三步，将上述所述的金属阵列放入预先准备的硅腔中，并将BOROFLOAT33玻璃与硅腔进行阳极键合；第四步，将上述键合好的两圆片在一个大气压下，对BOROFLOAT33玻璃加热，使其熔融，使其与上述的金属阵列很好的结合在一起，冷却，将上述圆片退火消除应力；第五步，去除生长碳纳米管的硅，最终得到用于微电子系统级封装的高密度转接板的制备方法。A method for preparing a high-density adapter plate for microelectronic system-level packaging, comprising the following steps: the first step is to grow a carbon nanotube bundle array on a silicon wafer; the second step is to use the above-mentioned carbon nanotube bundle Array metallization; the third step is to put the above-mentioned metal array into the pre-prepared silicon cavity, and anodically bond the BOROFLOAT33 glass to the silicon cavity; the fourth step is to place the above-mentioned bonded two wafers in the Under one atmospheric pressure, heat the BOROFLOAT33 glass to melt it, make it well combined with the above-mentioned metal array, cool, and anneal the above-mentioned wafer to relieve stress; the fifth step is to remove the silicon for growing carbon nanotubes, and finally A method for preparing a high-density interposer board for microelectronic system-in-package is obtained.
上述技术方案中，制备所述的碳纳米管束阵列的方法为，对洁净的硅圆片进行表面氧化，然后采用原子层淀积的方法淀积一定厚度的铝氧化层并且采用电子束蒸发的方法制作一层铁催化剂层，并对其进行光刻，最后通过CVD方法合成碳纳米管束阵列。制备出一批直径为5微米、20微米、50微米、100微米，间距为15微米、50微米、100微米、300微米的碳纳米管束阵列、第二步所述的对纳米碳管束金属化的方法为，首先将碳纳米管氧化，然后将碳纳米管放入活化液后，表面形成一层极薄的胶状体保护层，保护层下是催化活性晶核，将保护层去掉，暴露出催化活性层，最后将碳纳米管放入化学镀液中进行相应的金属镀覆。第四步将上述键合好的片子在一个大气压下加热至1270°C左右，例如选取为1200°C、1270°C、1240°C，保温3-8分钟，例如可以选取为：4 min，5 min，6 min，使玻璃与金属阵列结合起来，冷却，再在常温下退火消除应力，退火保温时间为30min，然后缓慢风冷至常温。第五步所述的去除生长碳纳米管的硅的方法为将退火过后的浸泡25%TMAH溶液中，以大于90°C的温度水浴加热，直至完全去除硅层。第三步所述的阳极键合过程中，硅片与玻璃基片按照阳极键合的工艺要求进行必要的清洗。 In the above technical solution, the method for preparing the carbon nanotube bundle array is to oxidize the surface of a clean silicon wafer, and then deposit an aluminum oxide layer with a certain thickness by atomic layer deposition and use electron beam evaporation A layer of iron catalyst layer is made, and photolithography is carried out on it, and finally carbon nanotube bundle array is synthesized by CVD method. Prepare a batch of carbon nanotube bundle arrays with a diameter of 5 microns, 20 microns, 50 microns, and 100 microns, and a pitch of 15 microns, 50 microns, 100 microns, and 300 microns, and the metallization of the carbon nanotube bundles described in the second step The method is as follows: first oxidize the carbon nanotubes, and then put the carbon nanotubes into the activation solution to form an extremely thin colloidal protective layer on the surface. Under the protective layer is the catalytic active crystal nucleus, remove the protective layer, and expose the Catalytically active layer, and finally put the carbon nanotubes into the electroless plating solution for corresponding metal plating. The fourth step is to heat the above-mentioned bonded sheet to about 1270°C at an atmospheric pressure, for example, 1200°C, 1270°C, 1240°C, and keep warm for 3-8 minutes, for example, it can be selected as: 4 min, 5 min, 6 min, to combine the glass with the metal array, cool down, and then anneal at room temperature to relieve stress. The annealing holding time is 30 min, and then slowly air-cool to room temperature. The method for removing the silicon growing carbon nanotubes in the fifth step is to soak the annealed 25% TMAH solution and heat it in a water bath at a temperature greater than 90° C. until the silicon layer is completely removed. During the anodic bonding process described in the third step, the silicon wafer and the glass substrate are cleaned as necessary according to the process requirements of anodic bonding. the
实施例4Example 4
一种用于微电子系统级封装的高密度转接板的制备方法，包括以下步骤：A method for preparing a high-density adapter plate for microelectronic system-in-package, comprising the following steps:
第一步，采用在硅圆片上生长碳纳米管束阵列；在硅衬底上旋涂一层20纳米的钛作为缓冲层，然后再钛上制备一层铝，再通过电子束蒸发的方法电极一层镍催化层，光刻，最后将上述衬底放入一个腔内，并且用40SCCM氢气和10SCCM氮气等离子体在850度条件下对上述衬底加工1分钟，备出一批直径为5微米、20微米、50微米、100微米，间距为15微米、50微米、100微米的碳纳米管束阵列。The first step is to grow a carbon nanotube bundle array on a silicon wafer; spin-coat a layer of 20nm titanium on the silicon substrate as a buffer layer, and then prepare a layer of aluminum on the titanium, and then evaporate the electrode by electron beam. layer nickel catalyst layer, photolithography, and finally put the above substrate into a chamber, and process the above substrate with 40SCCM hydrogen and 10SCCM nitrogen plasma at 850 degrees for 1 minute, prepare a batch of diameters of 5 microns, 20 microns, 50 microns, 100 microns, carbon nanotube bundle arrays with pitches of 15 microns, 50 microns, and 100 microns.
第二步，对上述所述的碳纳米管束阵列金属化；首先将碳纳米管氧化，然后将碳纳米管放入活化液后，表面形成一层极薄的胶状体保护层，保护层下是催化活性晶核，将保护层去掉，暴露出催化活性层，最后将碳纳米管放入化学镀液中进行相应的金属镀覆。 The second step is to metallize the above-mentioned carbon nanotube bundle array; first, the carbon nanotubes are oxidized, and then after the carbon nanotubes are put into the activation solution, an extremely thin colloidal protective layer is formed on the surface. It is the catalytically active crystal nucleus, the protective layer is removed to expose the catalytically active layer, and finally the carbon nanotubes are put into the electroless plating solution for corresponding metal plating. the
第三步，将上述所述的金属阵列放入预先准备的硅腔中，并将BOROFLOAT33玻璃与硅腔进行阳极键合；工艺条件为：温度400℃，电压：600V。 The third step is to put the above-mentioned metal array into the pre-prepared silicon cavity, and anodically bond the BOROFLOAT33 glass to the silicon cavity; the process conditions are: temperature 400°C, voltage: 600V. the
第四步，将上述键合好的片子在一个大气压下加热至1270°C左右，例如选取为1200°C、1270°C、1240°C，保温3-8分钟，例如可以选取为：4 min，5 min，6 min，使玻璃与金属阵列结合起来，冷却，再在常温下退火消除应力，退火保温时间为30min，然后缓慢风冷至常温。 The fourth step is to heat the above-mentioned bonded sheet to about 1270°C under an atmospheric pressure, for example, 1200°C, 1270°C, 1240°C, and keep warm for 3-8 minutes, for example, it can be selected as: 4 min , 5 min, 6 min, make the glass and the metal array combine, cool, and then anneal at room temperature to relieve stress. The annealing holding time is 30 min, and then slowly air cool to room temperature. the
第五步，去除生长碳纳米管的硅，最终得到用于微电子系统级封装的高密度转接板的制备方法。退火过后的浸泡25%TMAH溶液中，以大于90°C的温度水浴加热，直至完全去除硅层。 The fifth step is to remove the silicon on which the carbon nanotubes are grown, and finally obtain a method for preparing a high-density adapter plate for microelectronic system-in-level packaging. After annealing, soak in 25% TMAH solution and heat in a water bath at a temperature greater than 90°C until the silicon layer is completely removed. the
上述技术方案中，制备所述的碳纳米管束阵列的方法为，对洁净的硅圆片进行表面氧化，然后淀积一定厚度的铝氧化层和铁催化剂层，并对其进行光刻，最后通过CVD方法合成如图所示的碳纳米管束阵列。淀积铝氧化层的方法为原子层淀积，所述的制作铁催化剂层的方法为电子束蒸发，所述的CVD方法合成碳纳米管的工艺条件为：温度750°C，气流比率运用水蒸气辅助。第二步所述的对纳米碳管束金属化的方法为，首先将碳纳米管氧化，然后将碳纳米管活化，最后用化学镀的方法镀金属。第四步所述的玻璃加热温度为1270℃，退火温度为560℃，退火保温时间为30min，然后缓慢风冷至常温。第五步所述的去除生长碳纳米管的硅的方法为将退火过后的浸泡25%TMAH溶液中，以大于90°C的温度水浴加热，直至完全去除硅层。第三步所述的阳极键合过程中，硅片与玻璃基片按照阳极键合的工艺要求进行必要的清洗。 In the above technical scheme, the method for preparing the carbon nanotube bundle array is to oxidize the surface of a clean silicon wafer, then deposit an aluminum oxide layer and an iron catalyst layer with a certain thickness, and perform photolithography on it, and finally pass The CVD method synthesizes the carbon nanotube bundle array as shown in the figure. The method for depositing an aluminum oxide layer is atomic layer deposition, the method for making the iron catalyst layer is electron beam evaporation, and the process conditions for the synthesis of carbon nanotubes by the CVD method are: temperature 750 ° C, air flow ratio using water Steam Assist. The method for metallizing the carbon nanometer tube bundle described in the second step is to firstly oxidize the carbon nanotube, then activate the carbon nanotube, and finally plate the metal by electroless plating. The glass heating temperature in the fourth step is 1270°C, the annealing temperature is 560°C, the annealing holding time is 30 minutes, and then slowly air-cooled to room temperature. The method for removing the silicon growing carbon nanotubes in the fifth step is to soak the annealed 25% TMAH solution and heat it in a water bath at a temperature greater than 90° C. until the silicon layer is completely removed. During the anodic bonding process described in the third step, the silicon wafer and the glass substrate are cleaned as necessary according to the process requirements of anodic bonding. the
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