TW283738B - A new sintering process for A&N powder coated with Al film - Google Patents

Abstract

This patent application discloses a new process for preparing a sintering body with relative density greater than 95% can be observed on the specimens generate from AlN powder coated with Al film and sintered at 1650-1750 deg.C.

Description

283738 ^ 85.5. ^ Supplement "Λ a A7 B7 V. Description of invention () 1 With the demand for miniaturization and weight reduction of electronic products, semiconductor X industry is facing high-precision precision products such as integrated circuits and electronic systems. The requirements for high-performance, high-performance, high-speed, and high-efficiency development have increased, so the requirements for mounting these electronic zero-component substrates are becoming stricter. In general, the requirements for packaging electrical components for the substrate materials are as follows: Points: 丨. Has a high thermal conductivity, 2. Thermal expansion coefficient should be close to the thermal expansion coefficient of semiconductor component (cwp) materials such as silicon single crystal, 3. Dielectric constant and loss factor should be low, 4. High insulation resistance 10 15 Substrate materials that currently meet these requirements can be roughly divided into two categories, one of which is vaporized yttrium and broken glass (i> gt_〇Sin? _Mg〇_BrL), into BaSn (B ( Lh and other components are the main materials of the substrate manufactured by low temperature sintering. However, the remaining thermal expansion coefficient, dielectric constant, loss factor, and high insulation limit of this series of materials can meet the above conditions, but the low thermal conductivity of Qi becomes a major disadvantage. However, due to Because of the low cost and the ease of making substrates, scar merchants are still willing to develop substrates of such materials. M HI I-I mf tn ^ nn VJ -Λτ ^, -port (please read the back side first (Notes to fill out this page) Another type of material with high thermal conductivity is printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs. With the high and high functional density of integrated circuits, the computer has been made of a common integrated crystal (IC) progressed to LSI or even VLSI. During its operation, it can produce about 2 watts per square centimeter (W) of heat. These heat meters can dissipate and cause the entire path to fail to function properly. Such as oxidized wrinkles (such as ⑴, carbide (SiC), aluminum nitride (AlN) f high thermal conductivity substrate material was born at the historic moment 24. The thermal conductivity of beryllium oxide in such materials can reach 24〇w / nrk quite 20 2 ^ 83738 V. Description of the invention () 1 is ideal, but because the wood body contains highly toxic substances, it is not common, and only one businessman is still manufacturing it before. The material with carbon and silicon as the substrate has a thermal conductivity of up to 270 w / mk, and still need to add 1 wt% oxygen in manufacturing Beryllium (Be〇) helps it to be sintered around 1900 t: and must use hot pressing during sintering. It is not ideal for containing toxic compounds. It is produced only by Hitachi. High thermal conductivity can be added to the sintering aid at normal pressure, and it can be sintered under 1300 to form a dense sintered body. It is the most ideal material until H, so these materials are used as substrates to become various manufacturers ; 5L research institute research and development of the H standard. 10 However, in practice, aluminum nitride (Aj (N) there are some problems • For example, the inert sinking without the addition of pouring aids, must be about 24〇t: temperature Can obtain better sintering, so this kind of material is often prepared by hot pressing method into a dense state. Recently, HOBUYUKI'KIJRAMOTO was co-founded in Advance] · η Ceramics 15 Vol. 26, page 107. The powder used to control the particle size of the powder to have an average particle size of 1.5 wm and a particle size distribution greater than 5 α π accounted for at least 5 volumes I score, at〗, at a temperature of 900 ° C, 99% of the theoretical density can be obtained, the pure consumption of the Central Ministry of Economic Affairs of the Ministry of Economic Affairs, consumer cooperation du printing (please read the precautions on the back before filling out this page) aluminum nitride sintering body. And M.HIRAN0 et al., 1993, J. Mat. Sd. Vol. 28, No. 4725-30, reported that translucent aluminum nitride sintering can be obtained under atmospheric pressure to last for 8 min. It has a relative density of 99.6%. According to the paper by Jul ins C. SCHUSTER et al. Revne in 1987, such as 24 Chimie · Volume 24, page 676 • The following principles should be selected. Standard (CNS) A4 specification (210X297mm) 5. Description of the invention (5 10 15 f 5. Year A7 B7 Appropriate sintering aids, in order to prepare dense aluminum nitride sintered body under normal pressure. Substances that have chemical compatibility with aluminum nitride during the bonding process, that is, materials that can react with aluminum nitride to form a new solid phase or form a solid solution at high temperatures are not suitable. 2. At about 2,000 K Substances that form liquid phase to accelerate the densification-even when solid aluminum nitride is placed at the decomposition temperature, its diffusion coefficient is still low, so such sintering aids need to be added. 3. Substances with high resistance to avoid nitriding The crystal interface of aluminum is affected by a few phases and its insulation after sintering of aluminum nitride. Central Ministry of Economic Affairs Falcon The bureau employee consumer cooperation Du Printing 20 24 is currently engaged in the development of aluminum nitride substrates and materials. There are companies such as Toshiba, Tokuyama Takada, Japan Electric, Sumitomo Metal, and Hai Switzerland (this reaus), as well as some research institutions. The sintering aids used are various oxides, fluorides, vapors and other substances. The effects on the sintering of aluminum nitride are as follows. For the improvement of aluminum nitride under normal pressure (from N) The shortcomings of being difficult to entangle, add a sintering aid in the preparation process, and fire the dense sintered body by liquid phase sintering, then the added sintering aid finally forms the MG (3Y2〇3 · 5ΑΙ2〇.〇 phase or It shows that the γΑι〇3 phase accumulates at the intersection of the crystal grain interface, which is enough to cause the overall thermal conductivity to be affected. The company sells it under the Tosnite brand, and its heat transfer rate is about] 〇〇V / m · Κ υ and its comprehensive research institute also found aluminum nitride (from ^ effective sintering aid

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V. Description of the invention (1 In addition to: H and oxidation # 5 (Ca〇), there are also γί? 3 containing rare earth fluorides. 2. Add 3 needles of 3% of YPS at 1,800 l: temperature and normal pressure. N2 = junction for 2 hours in nitrogen, a substrate with a thermal conductivity of 180 W / mk can be obtained. The substrate with a thermal conductivity of 17〇5 WAn · k can also be obtained by adding 7 wt% under the same conditions. Two kinds of sintering All kinds of different phases such as YAG, X3, Α1Λ〇9, etc. can appear at the intersection of different crystal grain boundaries or at the grain boundaries, and the benefit shows a proportional increase with the added content of γ2〇3. Observational microscopic observation (SEM) of the knot body shows that the addition of} wt% of ~ 〇3 is accumulated in the liquid phase in the grain boundary, and the addition of 3 wt% is stored in the grain boundary 3 junctions in the state of 10 burn The thermal conductivity of the structure is better than that of the added amount. (Please read the notes on the back before filling out this page) A-Yideshan Caoda Co., Ltd., develops a primary particle diameter of about 1 0.6 " m, the average particle size after agglomeration is about 14 Aluminum Nitride (N) 15 powder technology. No sintering aid added by hot pressing method at 175 ℃ It forms a serpentine dense body, while the high temperature reaches 1,9⑻ ~ 2, 〇 such as t at atmospheric pressure τ into the sintered body * its sintered body can be densified to 95% of the theoretical density and the heat transfer rate is 140 W / VK. Cangyuan Xinxing even used Ca (N〇3h sintering aids and found that the calcium aluminate phase was sintered during the sintering process. 20 1,800 ° C for 3 hours can entangle the dense sintered body. · Zuo Metal Industry Central Institute of Technology Gao Weizhe studied the relationship between the sintered body crystal particle diameter and thermal conductivity, and found that the sintered body with high thermal conductivity has a fine structure. Add 0.5 ~ 3 v / t% dagger 〇3 is a sintering aid 5 This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297mm)

'1T Ministry of Economic Affairs Central Standard Falcon Bureau Employee Poverty Alleviation Cooperative Printed for £ 8

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73S 1. Description of the invention (The sintering temperature is set to 1,700 PC, 1,800 ° T, 1,900 ° C, respectively, and it is masked in nitrogen for 3 hours at normal pressure. After TgM Observation with scanning electron microscopy (SEM) shows that there is a yag phase at the triple junction of the grain boundary, and the results are consistent with the Toshiba company. The sintered body is added at a temperature of 1,900 C at 3% The sintered body obtained by sintering has a thermal conductivity of 122 w / k. M Printed by the Consumer Cooperation Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs and printed by Thomas B. et al.] 9δ9 J.Ara.Ceram.Soc. Volume 22 The 8th issue, pages 489-91, was published with the addition of sintering aids mixed with γ2〇3, calcium oxide (ca〇), IOUWh, plutonium oxide (ce〇2), and silicon dioxide (Si〇2). The characteristic method of firing the dense system at 1,600 t. The current development of aluminum nitride sintering technology in the industry is described in various patents; Deshan Caoda Co., Ltd. 1992 No. 4928928 This patent discloses that adding 5 wt% Υ203 and organic binder to aluminum nitride powder, coating the surface of the formed blade with high melting point metal powder glue The body is heated and sintered in nitrogen at 1,800 C for 5 hr. A method for preparing a sintered body. Kyoto Ceramics Japanese Patent No. 3-1Q3,56Q, published in 1⑽ 1 year, discloses that aluminum nitride is the main component added by 0.1. ~ 1 5 wt% rare earth 20 aluminum compound, and a black agent containing metal thallium or carbonized thallium, sintered in nitrogen at 1,820 t: temperature for 3 hr * to form a black aluminum nitride sintered body. 24 Toshiba Corporation Japanese Patent Disclosure No. 3-279264 No. 3-279264 published in 1991 (please read the precautions on the back before filling in this page). Stupid. -4 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) , A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs 5. Description of the invention () 1 shows that the aluminum nitride powder is molded without the addition of sintering aids. The binder is removed before 700 ° C. At normal pressure Introduce nitrogen gas at (1 atm) and continue at a temperature of 1800 t through hot pressing (HP). Sinter for 4 hr 4 and place it in a carbon clamshell to raise the temperature to 1,900 t for heat treatment for 6 hr to make a high thermal conductivity sintered body 5 methods of preparation and transfer. In 1992, Japanese Patent No. 446060 on coloring nitrogen The patent for aluminum sintered body and its manufacturing method is based on the addition of earth compounds and 0.5 to 10 wtk rare earth compounds to aluminum nitride> sintering in nitrogen at 1, milk 0 ° C for 48 hr. 10 Chuanling Japanese Patent Publication No. Hei 4-0172 of 1992 by the Iron and Steel Co., Ltd. discloses that adding 5 wt% of the molded body of γ2〇3 to 1,90 in boron nitride (BN) or boron nitride and aluminum nitride containers ° C temperature burned for 4 hr. The patent of Sumitomo Electric Industries Co., Ltd. in 1992, No. 4-92867, regarding the high thermal conductivity coloring nitride sintered body and its manufacturing method, is the addition of 〇05 ~ 15 0.5 v / t% carbon-containing boron to aluminum nitride Compounds, rare-earth aluminates below 0.01% by weight, at least 0.01% to 0.15%, at least one or more compounds selected from the elements of group ivr, vb, and VIB in the periodic table are sintered to form a sintered body with color. Kanamakis Co., Ltd. (MM) Co., Ltd. revealed the Japanese phase of the Japanese Patent No. 4Q6503, the surface of the secretive aza (sub) is protected by the rear 20-a method for preventing the reaction between the nitrogen nitrate and water . According to the information in the data, it can be seen that most of the 11-day conversion methods in the past except its "No. 446060 profit-making without adding sintering aids are more special 24, the rest are all added with sintering aids with oxides or non-oxides, and Control (please read the precautions on the back before filling in this page) (η 装 _ Order • LO. 7

Du Printing Co., Ltd. Employee Consumption Cooperation of the Central Standards Bureau of the Ministry of Economic Affairs 1 Liquid phase sintering at a temperature above 1800 ° C. Addition of oxide systems such as YHaO ..., or non-oxide systems such as PY, PL, Yc, etc. to these Buddha preparation methods, resulting in the formation of other phases of the compound and remaining in aluminum nitride (AKN) The phenomenon of reducing thermal conductivity in the sintered body. Even if the sintering aid is added in the 5th-level manufacturing process, a sintered body with a sintered body of more than 1800 t can be obtained. Adding a binder attributed to organic substances during the bonding process, even if it takes a considerable amount of time to carry out the decarburization work, there is still a phenomenon that free carbon remains and affects the quality of the substrate. 10 In view of this, the inventor has made a keen inspection and research, and found that only the surface of the aluminum nitride (ΑΪΝ) powder particles is covered by a subsequent layer of aluminum (ΑΪ), which is formed by the forming machine or preliminary forming and then cooled. Pressure equalization, a method for obtaining a dense sintered body without adding any sintering aid. This method does not require the addition of entanglement aids. * No organic materials such as sintering agents are used, so no other phases remain in the sintered body of Xinghua Ming 15, even if it does not need to be decarburized for a long time, it will not be troubled by residual carbon The thermal conductivity of the sintered body and the quality of the substrate are not affected by it. The sintering temperature of the method of the present invention is only 1650 ~ 1750 t and the current 1800 t: it is lower, and the dense sintered body can be fired at a holding temperature of 3 ~ 6 hours, and the density can be close to the theoretical value. 20 The present invention is applied to the surface of aluminum nitride (AtN) powder particles after being coated with aluminum (Aj〇 film *), which is a simple way to use vacuum evaporation film, which can be easily coated on the surface of aluminum nitride powder particles in a short time Aluminium film. The method of covering the aluminum belly can be revealed by 24 A. Grisei et al. In 1989 Chem. Sen. Tech. No. 2 8 This paper size is applicable to China National Hua (CNS &A; A4 specifications (210XW7 mm > (Please read the precautions on the back before filling out this page)

283738 V. Description of the invention (sputtering, or other conventional chain film pudding such as dip coating & (dipping), spin coating method) • These key films take a little longer. Applicable The aluminum nitride (⑽N) powder in the present invention can be prepared in various ways, for example, by reduction nitridation method, or by heating and nitriding the aluminum metal powder, or using the gas phase method to prepare the aluminum nitride powder, flame method or Other coating. The manufacturing method of the aluminum nitride surface coated aluminum film of the present invention printed by the Central Standard Falcon Bureau Employee Consumer Cooperative of the Ministry of Economy guarantees the manufacturing method of the sintered body obtained by the low temperature of the nitrided powder coated metal aluminum belly at low temperature, mainly 10 The purpose is to not need to add sintering aids, and can obtain a more pure sintered body to achieve a compact skin at a lower temperature. The manufacturing method of aluminum nitride surface coated aluminum film of the present invention, followed by | The heterogeneous sintering aids to reduce the sintering temperature, because the sintered body has no other phase residues, so it is affected by the thermal conductivity or quality of the sintered body. The aluminum nitride surface of the present invention is coated with aluminum belly Manufacturing method, the main manufacturing process is shown in Figure 1. The raw material aluminum nitride (A 〖N) powder can be prepared according to various methods. The method is prepared by the gas phase method. The average particle size of the powder is only 0.7⑽. It is easy to cause agglomeration due to electrostatic adsorption, and the oversized agglomerates must be sieved first. If the mesh is too small, the fen body can be easily condensed after being coated with aluminum film; if the mesh size is too small, the agglomerate 9 This paper size is applicable to the Chinese national standard (CNs) A4 specification (210X297 mm) (please read the precautions on the back Fill in this I) again.

.1T Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 2.83738 A7 B7 V. Description of invention (1) Most of the differences are small, and the most suitable sieve bundle in the work that affects the uniformity of afterheating is the No. 100 sieve ( mesh) · The re-condensation phenomenon presented in the process is not serious, and the size of the condensate is not very different. r- ^ / 'N Γ powder screening LJ vacuum vapor deposition k_— J _ > dry press forming L ^ r · > sintering {a »wide— · cold equalizing pressure ___> 10 The surface of the aluminum nitride powder particles deposited by vacuum evaporation is engraved with aluminum. The evaporation equipment used is as shown in Figure 2. The aluminum nitride powder is placed in a specific container and placed in a vacuum chamber. Weigh a certain amount of metal aluminum wire Hang on the heated tungsten wire 15. Carry out vacuum extraction of pomelo, and when the vacuum degree reaches 1 (Γ4 ~ 1 (Γ5 torr, make the powder to be aluminized to the amount of aluminum to be quilted. The aluminum nitride powder that is warmed by the aluminum is pressed and formed by a hydraulic press. Then press it with cold equalizing pressure. The formed specimens are placed in a gas boron crucible covered with boron nitride (BN) powder and placed in a high-temperature furnace to remove the residue in the wall of the chamber and the chamber. Oxygen and water vapor, then use 99.9% high-purity nitrogen. Maintain the pressure of the reaction chamber at 1.04 atm, raise the temperature to 750C for 2 hr, and then rise to 1450 t! Earn the temperature for 3hr, and then rise to the set temperature Hold liquid at 24 ° C for liquid phase decoction. 10 The paper size is suitable for China National Standard (CNS) A4 (210X297mm) (please read the precautions on the back and then fill in this page "Finishing · Order A7 A7 Central Standard of Ministry of Economic Affairs Falcon Bureau employee consumption cooperation Du Printed V. Description of the invention () 1 In the above manufacturing method, the price of the rear aluminum heating is related. In order to achieve the vacuum skin of the vacuum chamber, ϋ often uses a rotary mechanical pump for rough pumping. The vacuum degree is 2 ~ SXlO ^ torr, and the valve must be opened slowly to prevent the powder from being released. Help the diffusion pump to a vacuum of less than 2~5X10-4 torr. 5 to achieve uniform powder deposition effect of the body need • meal was spread evenly over the vessel steaming bond

After cooling, the aluminum powder is turned upside down, and the evaporation is repeated again to achieve the required amount of coated aluminum. D According to the manufacturing method of the aluminum nitride surface coated aluminum film of the present invention, 10 aluminum nitride test pieces can be tested The density of green embryo, density of sintered body, etc., linear shrinkage rate before and after burning casks, specific dielectric constant (k), loss factor (fanδ), insulation resistance coefficient (/ 〇), thermal conductivity, grain size, etc. "Physical and Electrical Testing" and the use of X-ray diffraction (X-ray diffraction), scanning electron microscope observation (SEM), electron microprobe analysis (ΕΡΜΑ), penetrating 15 electron eigenmirror structure analysis (STEM ) And other methods to analyze the structure of Huan. X-ray diffraction of the starting material aluminum nitride powder, pressed into a sheet shape as a vapor-deposited metal aluminum strip, aluminum nitride powder coated with aluminum alloy, and sintered aluminum nitride sintered body, the results are shown in the figure Four shown. In the diffraction pattern of the aluminum nitride 20 powder of the aluminum film, several weak diffraction peaks are found in the diffraction pattern of the starting material aluminum nitride, and the weak diffraction peak is The diffraction peak position of aluminum metal confirms that after the aluminum nitride powder is vapor-deposited, the metal aluminum is indeed coated on it. Observe the diffraction ring of the sintering ring again, we can see that the test piece is characterized by a weak metal aluminum around the 24 peaks, which has completely disappeared after sintering, proving that the surface metal aluminum has been sintered to 11 (please read the notes on the back first Please fill out this page again)

, 1T This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X29 * 7mm) 28 A7 B7 Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Description of invention () 1 Completely converted to aluminum nitride. Compare the diffraction pattern of the sintered body with the original aluminum nitride powder • It can be found that the cast body is at 20 = 26.69. There is a weak diffraction peak. According to Takahashi Takahashi et al.'S high heat conductivity in 986, a special feature published the sintering mode of aluminum nitride without added sintering aid, indicating that the surface of the particles of aluminum nitride powder 5 itself has a small amount of alumina protection After the layer is sintered at a temperature below 2,000K, a solid solution phase of aluminum oxynitride (Spinel, A10N) can be formed with aluminum oxide at the interface of the aluminum nitride particles, from which it is speculated that the sintered body is weakly diffracted The peak should be the solid solution phase of the aluminum oxynitride (A10M) at the grain interface, or the aluminum film deposited by the envied aluminum film in contact with the air to form an aluminum oxide (Al2〇3) compound 10 ° according to the present invention aluminum nitride surface The manufacturing method of the coated aluminum belly, the prepared aluminum nitride test pieces with different amounts of aluminum film coated, respectively, were sintered at 1700 UC and 1750 UC for 3 hours * The linear shrinkage of these sintered bodies ( 15 Linear Shrinkage, LS.) And the relative density (RD., Realitive Density) and the relationship between the amount of star is shown in Table 1 and Figure 5, during which the amount of aluminum film is not gradually increased to the amount of coated aluminum In the [[5 or so can be close to the theoretical value, and the amount of aluminum is higher than 1.5 wt,% regardless of the relative density Or the linear shrinkage rate tends to be unsatisfactory, which shows that it is helpful for the sintering of 20 aluminum nitride in a certain amount range. Even if the excessive amount of envied aluminum is not beneficial to the sintering of aluminum nitride, it will hinder its sintering. At 1700 t: the sintering temperature is 1.5% v / t% aluminum nitride (24 A1N) sintered body, the relative density can reach 90.54% of the theoretical value. Standard (CNS) A4 specification (2H) X297 public envy) '' (Please read the precautions on the back before filling this page)

* 1T ό A7 B7 printed by the Employee Consumer Cooperative of the Central Department of Economic Affairs of the Ministry of Economy V. Description of invention () 1 Shrinkage rate is about 13. Increase the temperature to sinter at 750 ° C. Except for the amount of aluminum to be 5 wt%, the rest of the test pieces are higher than the 1700 temperature sintering regardless of the relative density or linear shrinkage. From about 1 wt% to 3 wt%, the relative density in this interval is higher than 5 90% of the theoretical value, of which the best weight is 1.5 wt%, which can reach 95.09% of the theoretical value, linear shrinkage There is also 16.67%. The sintering results of aluminum nitride coated with different amounts of aluminum film at 1,750 Ό sintering temperature for 1, 3, and 6 hours are shown in Table 2. The relative density of 10 and the shrinkage rate of the aluminum alloy are The relationship is shown in Figures 6 and 7. The aluminum nitride coated with different amounts of aluminum film was sintered at a temperature of 1 hour. Although the density and linear shrinkage of the sintered body were obviously low * However, it was between 0.67 ~ 2, 12 wt% without a quilt. The aluminum film is better than the aluminum nitride that is not warmed by the spring aluminum, which shows that the hooded aluminum belly is helpful for the sintering of aluminum nitride. Among them, 1.3 wt% is best for the heat of the aluminum 15 after being sintered. The density_ is 77.91% of the theoretical value, and the linear shrinkage is 13.17%. The sintering density of the sintered skeleton can reach 95.09% of the theoretical value with 1.5 wt% of sintered aluminum after sintering for 3 hours. The linear shrinkage rate is also 16.67%, so the ideal amount of coated aluminum is about 0.67 ~ 2.8 wt% . Due to the longer holding time, the density and linear shrinkage ratio of the sintered body tended to be more theoretical, and as a result of holding the temperature for 6 hours, the effect of the amount of aluminum film on aluminum sintering was more obvious. When the amount of aluminum to be polished is 3.53 wt%, the density is 76.38% of the theoretical value, the linear shrinkage is only 7.67%, and the test piece with the amount of 0.43% and 1.5 wt% is coated with Zhao 24 Density is up to 99%, 99.39%, and the linear shrinkage rate is 13 pieces of paper U Shicai Guanjia specifications (210Χ297 ·:;? T ---------- Ck ---- --IT ------ ο (please pay attention to the matters on the back of wtt before filling out this page) ^ S3738 A7 B7 Central China Bureau of Economic Affairs Employee's Consumer Cooperation Du Printed Fifth, Invention Description () i M.67% From these results, it can be judged that 0.47 ~ 1.5 wt% of aluminum film is sintered on aluminum nitride powder, and sintering at a temperature of 1750 t for 6 hours can obtain a quite dense aluminum nitride sintered body. The sintering results of the test pieces containing more than 2.5 wt% of smilax aluminum at a temperature of 3 hours and 6 hours found that the test pieces held at a temperature of 6 hours in terms of density or linear shrinkage were worse than those held at a temperature of 3 hours, which proved to be When the amount of post-aluminum is too much, it will hinder the sintering of aluminum nitride. Therefore, the amount of thin aluminum in a certain area can promote the casting of aluminum nitride, and this area is widened with the increase of the temperature when the temperature is maintained. 10 The measured volume should be a function of the holding time and temperature time. The aluminum structure of aluminum nitride with different amounts of aluminum coated at 1700 ° C can be obtained by holding the temperature for 3 hours, as shown in the photo (1) In the photo (Ι-a), it is pure aluminum nitride with no coating and quantity, there are 15 images between the particles, there is a significant size difference between the grains, and there are more pores (pores) ), Its grain boundary is not obvious, etc. • It can be determined that its sintering is incomplete. The sintering temperature of this system is too low and there is no liquid phase to help the rearrangement of the particles, the diffusion rate is very slow, only the denser particles are closer to the islands. The grain growth causes a significant gap between the grains. The density is only 85.89% of the theoretical value, and the linear shrinkage 20 rate is also reduced to 10.47%. The photo (Ι-b) is the amount of coated O.67wt% aluminum The microstructure of the test piece, which contains fewer holes than the photo (Ι-a), and the grains are more obvious and larger. This grain boundary can be clearly identified. The density is slightly increased up to 87.42 of the reasonable value % 14 (Please read the notes on the back before filling this page)

Order 0 This paper scale is applicable to the Chinese National Standard (CNS) A4 &# (210X 297mm) Printed and printed on the A7 & Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs A7 ------------ B7 V. Description of invention () &Quot; ~-1 photo (〗 ~ c) is the characteristic structure of sintered impurities obtained after 1700 " 0 burned mackerel with about 1.5 wt% aluminum content after quilt, and its density is 90.59% of the theoretical value is this part The highest. The sign (H) of the photo (H), the surface of the shaft is more than (b b, b c) * However, there are many sign cracks, and there are also some nitride particles at the grain interface and cracks. The photo (1_e) is a sintered body with an amount of 5 cores of aluminum. Because the amount of aluminum is too much in the sintering process, the resulting cracks and excessive nitride particles are too large, which hinders the sintering of the nitrided button . The microstructure of the cross-section of the sintered body was kept at a temperature of 750 " C above the same coating amount for 10 3 hours, as shown in the photo (2). It was found that the amount of pores in the photograph (2) generally decreased and the grain 1 was now growing. It was confirmed that the density of the sintered body at 175 ° C was better than that of the sintered body at 170 ° C. The density of the sintered male with 0.67 wt% inscribed amount is lower than that of 2.8 wt% aluminum, which is the opposite of the inert shape sintered at 170 ° Ί〇 described in the photo (1). In addition, 15 was envied by too much aluminum film: the microstructure photo of the beginning of the mass sintering, it can be found that the washing and cleaning of υςοΡ is generally less than the dare to disperse the remaining paper particles on the surface of the large grain. The structure of the cross-section of the cast body obtained by holding the temperature for G hours compared with the photograph (2) is shown in the photo (3). Due to the extension of the temperature holding temperature, the diffusion effect of aluminum after 20 was increased, so that the number of holes in the test piece held at the temperature of 6 hours was reduced, and the particle size was slightly increased. However, the grain boundary was still blurred and the density was not high. Only 89.87% of the argument value. In the photos (3_b) and (3-c), almost no rolling holes can be seen, and the average particle size is about 2 "m left and right, there is also a significant increase phenomenon, which belongs to the phase 24 when the dense late junction body can be compared with the relative The test value with a density of 99% or more is 15. This paper scale is applicable to the Chinese National Standard Falcon (CNS) Α4 specification (2 丨 〇X 297mm) (please read the note on the back first and then fill in this page) A. Order A7 B7 283738 V. Description of invention () 1. Correspondence. The photo (3-e) is a test piece with too much aluminum, which has been improved. The photos (1 -e) and (2-e) aluminum nitride grains have nitrogen on the surface. The phenomenon of aluminum oxide particles and flakes, which are combined in the shape of small grains on the surface of the grain. 5 To evaluate the manufacturing method of aluminum nitride on the surface of aluminum nitride according to the present invention " aluminum nitride. It can be applied to electronic packaging substrate materials, so the basic requirements of substrate materials such as insulation resistance, dielectric coefficient, loss factor, thermal conductivity ... are measured. 10 Test with 25 voltage and charge 30 sec. Conditional use HP • 4329 A high resistance meter to measure the resistance coefficient, as shown in Table 3, the resistance coefficient value of sintering ceremony, There is the same trend between the degree and the resistivity, showing that the sintered body with higher density has a higher electric limit coefficient, of which 15 wt% is ideally sintered from the aluminum heating test piece after about 1700 t. The preferred value of the electrical limit system 15 is about 5.94 > < 101 () Ω-cm, and its value after sintering at 1750 t is SjXlOHQ-cm, which is within the insulation free range. Even at 1750 ° C The test piece sintered with a proper amount of aluminum after being sintered at a temperature of 1 hour, as shown in Table 2, the highest density can only reach 77.91% of the theoretical value, and the electrical coefficient of 20 is only 10] ° as shown in Table 4. ° Ώ-cro The test piece whose density can reach more than 95% after burning at a constant temperature for 3 or 6 hours • The electric limit coefficient has a value of 1011 Ω-cni grades of insulating fluorine. 24 To reduce the delay speed of signal transmission in the circuit Therefore, the Chinese National Standard (CNS) A4 specification (210X297mm) is applicable to the 16 paper standards (read the precautions on the back and then fill out this page)-* β Ο Printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs 738 A7 __ B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The substrate material of the substrate should be pursued with a low dielectric constant teaching "T: holding the temperature for 3 hours to sinter different aluminum after the sintering, the difference in density of the test piece is large, resulting in sintering as shown in the eighth The protection charts of the specific dielectric constant, loss factor (tan δ) and amount of smilax aluminum show a significant difference between the specific permittivity and loss due to the value of 5. The amount of aluminum after being tested is 15 wt% The specific dielectric constant exhibited by the film is 12.09, and the loss factor is about 0.2813 (ΙΚΗζ), indicating that the higher the density of the test piece, the higher the dielectric constant and the loss factor tend to be the ideal 簌 园. The temperature at 1750 t: the same trend was obtained, but the difference in dielectric constant and dissipation factor between the test pieces with different amounts of Smilax aluminum was smaller than 10. The prolonged temperature holding time shows the difference in specific permittivity and dissipation factor for different amounts of aluminum nitride and aluminum, and there is no great influence. As shown in Figure 9, the dielectric constant and The relationship between the amount of coated aluminum and the relationship between the loss factor of the sintered body and the amount of aluminum to be shown in Figure 10. The optimal sintered body at a temperature of 3 and 6 hours has a dielectric constant value of 97%, 10.81 The lowest 15 loss factor value is 0.0722, and the temperature maintained for 6 hours is 0.0173 and 0.0240. Both are test pieces with relative density greater than 95%. Miniaturized electronic products have high-density body circuits and electronic systems that operate at high speeds. The electricity generated by the components generates a lot of heat. Therefore, the material used as the substrate must be sufficient to dissipate the heat of the component and reduce its thermal conductivity. * To avoid donating the characteristics of electronic components. The manufacturing method of "aluminum nitride surface of the present invention" is "aluminum nitride surface" and "aluminum content 2.12 Wt% at 1750 sintered for 6 hours. The above test revealed that the relative density g7.55% is on commission 24 The thermal conductivity value obtained by the Institute of Industrial Technology's laser flash test is 12〇w / mk. 17 This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm ---------- 0 ^ ------, 玎 ------ 0 (please read the back Please pay attention to this page and fill in this page} A7 B7 1 V. Description of the invention (., As mentioned above, according to the present invention " Aluminum nitride surface coated aluminum film manufacturing method. After the surface of the nitride powder is warmed by strict metal aluminum, Directly by forming 1; applying the pressure equalization step and placing it under normal pressure at a temperature of 1650 ° C ~ 1750 P which is lower than the known temperature to form a compact aluminum nitride cast body. Since this method does not use sintering aids, it can save the time of adding sintering aids and granulation time, and it is more trendy in the manufacturing process. The sintered body has been observed by various structural features and analysis of properties to confirm the pouring The body possesses excellent traits that meet the needs of the industry. 10 In order to make the purpose, method and advantages of the present invention more obvious, the following specific examples are given as detailed and specific statements, but they are not limited by their contents. (Please read the back of the page; i will fill out this page if you want to pay attention) Install,-»15 Central Ministry of Economics Falcon Employee Consumer Cooperative Prints $ !. 20 24 Illustrated Figure 1 Manufacturing Process 1. Vacuum suffocation 11. Electrode 12. Tungsten Gun 13. Cultivation m 14. Pelarney Vacuum Gauge 2. Expansion 21 .. Water outlet 22 .. Cold water inlet 3. Ion vacuum fiber 4 .. Vacuum chamber 5 .. Mechanical pump ring 2. Vacuum evaporation device ring 3. Back ventilator flow circle Figure 4. X-ray diffraction 1. Raw materials Vaporized aluminum 2. Metal aluminum 3. Aluminum nitride powder after the aluminum belly 4. Sintered aluminum nitride sintered to catch the jade sintering "The relationship between the density of 4 phases, the linear shrinkage car and the amount of aluminum Figure (3 hours of earning warmth) 1700 1〇 ☆ Relative density * Linear shrinkage 175 (TC □ Relative density + linear shrinkage 18 " i. This paper scale applies the Chinese National Standard (CNS) A4 specifications (2 丨 0X297mm

V. Description of the invention () The relationship between the relative density of the six sintered sterns and the amount of aluminum after being printed in the printing circle of the employee consumer cooperative of the Zhongshen Falcon Bureau of the Ministry of Economy (1750 1C sintering temperature) + earning 1 hour □ earning 3 Hours * 6 hours of overflow Figure 7 The relationship between the linear shrinkage of the sintering ceremony and the amount of gray aluminum. Figure 5 (1750 C sintering temperature) t holding temperature 1 hour □ holding temperature 3 hours * earning temperature 6 hours threshold eight sintering Relationship between volume ratio dielectric constant, dissipation factor (tan 0,) and the amount of aluminum to be treated (temperature 3 hours) 1700 V □ specific dielectric constant + dissipation factor 1750 ° C * specific dielectric constant dissipation factor ° diagram Diagram of the relationship between the dielectric constant of the nine-burning body and the amount of aluminum affected (sintering temperature at 1750 ° C) * Earning temperature 1 hour + earning temperature 3 hours □ Earning temperature 6 hours Figure 10 Ratio dielectric constant of sintered body 、 The relationship diagram between the loss factor (tanδ) and the amount of aluminum to be removed (sintering temperature at 1750 ° C) * Temperature for 1 hour + Concentration for 3 hours □ Temperature for 6 hours Table, photo description table) After sintering at 1700 1〇 and 1750 ℃, the density, relative density and linear shrinkage of the sintered body A winding temperature = 1700 t B sintering temperature = 1750. 〇Table (2) Winding results of different surplus at 1,750 ° C for 1, 3, 6 hours holding temperature (2) 1700 ° C and 1750 t for 3hr, resistance coefficient value of gasification and sintering ceremony Table (4) The resistance coefficient value of sintered gas at 1,750 aC for 1, 3, 6 hours, sintering ceremony 4 19 This paper scale is applicable to the Chinese National Standard (CNS) Λ 4 specification (210X 297 mm) (please read first (Notes on the back then fill this page)

A7 A7 B7 printed by the Employee Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs 5. Description of the invention () Photo (1) Aluminum nitride with different amounts of aluminum after being sintered. (a) 0.00 wt% (b) 〇, 67 wt% (c) 1.50 wt% (d) 2.80 wt ^ (g) 5.〇〇wt% photo (2) coated aluminum aluminum nitride with different amounts of ; [750 Sintered Zhao with its temperature held for 3 hours • Sem of its profile (a) 0.00 wt% (b) 0.67 wt ^ (c) 1.50 wt ^ 10 (d) 2.80 wt% (e) 5.00 wt% photo ( 3) The aluminum nitride with different amounts of aluminum is washed at 170 ° C for 6 hours. The cross-section is (a) 0.00 wt% (b) 0.43 wt% (c) 1.5 wt ^ (d) 2.4 wt% (e) 3.53 wt% 15 Example 1 3 g of aluminum nitride (AIN) powder was first sieved through a loo screen, evenly distributed in a Petri dish, placed in a vacuum chamber and weighed 0.1 g of aluminum wire, Hang it on the tungsten wire heated at 20, and wait for the vacuum to reach 10-4 ~ 10_ε torr. The current is adjusted to 50 amperes (Λ) and the voltage is 3 v. When the aluminum is completely melted, turn off the power for 40 seconds. After cooling, turn the powder over. According to the amount of aluminum needed, keep on repeating I. 24 Take 1 8 of 1.5% by weight coated aluminum nitride nitride powder, and place it on a paper with a diameter of 20. The standard size is r 圅 庅 塅 堈 芈 (CNSy A4 specification (210X297mm) (please read the notes on the back first Fill in this page)

A7 B7 V. Description of the invention (1) In a 1.5 cm stainless steel mold * Use a hydraulic press to dry-press molding at a pressure of 15 kg / cm2 • Then apply cold equalization pressure under a pressure of 2000 kg / cm2 to earn 1 point Form a test piece. 5 Place the test piece in a boron nitride (BN) crucible in a vacuum furnace of 2 > < 10 ~ 4 torr vacuum shape, slowly increase the temperature to 300, pass 99 9% atmosphere, and hold the pressure of nitrogen at 1.04 atm and heated at a rate of 10 to 750 C for 2 hours, then at a rate of 5 C / min; [, 45〇t: held for 3 hours, and finally heated to 1700 at a rate of 2.5 tVmin Warm for 3 hours. Examples 2 to 20 According to the method of Example 1, various 15 pieces were produced according to the conditions shown in Table 5. (Please read the precautions on the back and then fill out this page)-* Printed by the Consumer Labor Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs 20 24 21 This paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm)

Claims (1)

6. Scope of patent application • A method for sintering low-temperature aluminum nitride (ALN) into a dense aluminum nitride ceramic sintered body: using aluminum nitride particles or aggregates with a surface metal A1 amount of 0 · 1 ~ 5wt%, After pressure forming and sintering, first heat under vacuum to melt A1 and connect it between the aluminum oxide particles, and keep the temperature for a period of time, then pass a gas that can nitrify the metal aluminum into aluminum nitride. The temperature is increased, and then the temperature is increased from 1650 to 1750 sintering temperature to produce a dense aluminum nitride ceramic sintered body. --------- ί ------ IT ----- ^ — Μ I (Please read the precautions on the back before filling out this page) Printed copy of the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210 X 297 mm)