WO2021060348A1 - 導熱層の製造方法、積層体の製造方法および半導体デバイスの製造方法 - Google Patents
導熱層の製造方法、積層体の製造方法および半導体デバイスの製造方法 Download PDFInfo
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Definitions
- laminated LSIs As the performance of three-dimensionally laminated LSI devices (hereinafter, also referred to as "laminated LSIs") is improved, the problem of increased power consumption and heat generation due to the increase is an important issue in design technology and packaging technology. It is becoming.
- the heat generated from the inner LSI device may not be properly dissipated by the conventional method of dissipating heat from the package surface. If heat dissipation is insufficient, the temperature inside the laminated LSI will rise locally, and the characteristics of the transistor will change due to the high temperature. Therefore, there are concerns about an increase in leakage current leading to an increase in power consumption and a malfunction of the circuit. Further, heat has various adverse effects not only on the laminated LSI itself but also on the electronic device in which the laminated LSI is incorporated. Above all, attention should be paid to the impact on safety, performance and reliability (eg, reduced operating speed and life).
- Patent Document 1 contains a carboxyl group-containing copolymer resin, a photopolymerization initiator, an inorganic filler having a thermal conductivity of 15 W / m ⁇ K or more, and the content of the inorganic filler is a solid content.
- a curable resin composition having an amount of 80% by mass or more is described therein. It is described that such a curable resin composition is excellent in thermal conductivity and moisture resistance, and is useful for a resin insulating layer in a package substrate or a surface mount type light emitting diode.
- Patent Document 2 describes a dry film solder resist obtained from a resin composition and a circuit board containing the dry film solder resist. Then, it is described that the resin composition contains an acid-modified oligomer, a photopolymerizable monomer, a thermosetting binder resin, a photoinitiator, two or more kinds of spherical alumina particles having different particle sizes, and an organic solvent. ing.
- composition for forming a heat conductive layer for forming a film (heat conductive layer) containing a filler and having thermal conductivity and electrical insulation as described above.
- One method is to dissolve all the components of the heat conductive layer forming composition in a solvent, apply this to the support by a wet process such as a spin coating method, and dry the applied material.
- the distance between the fillers inside the heat conductive layer after drying may not be in an appropriate range, and the thermal conductivity and electricity of the heat conductive layer may not be appropriate. Insulation may not be exhibited properly.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a method for manufacturing a heat conductive layer that enables the heat conductive layer to appropriately exhibit its thermal conductivity and electrical insulation.
- Another object of the present invention is to provide a method for manufacturing a laminate and a method for manufacturing a semiconductor device to which the above-mentioned method for manufacturing a heat conductive layer is applied.
- the above problem could be solved by devising the conditions for applying the composition for forming a heat conductive layer onto the support. Specifically, the above problem was solved by the following means ⁇ 1>, preferably by the means after ⁇ 2>.
- ⁇ 1> Using a composition for forming a heat conductive layer containing a resin, a filler and a solvent and having a solid content concentration of less than 90% by mass, a heat conductive layer having a thermal diffusivity of 3.0 ⁇ 10 -7 m 2 s -1 or more was formed. It is a manufacturing method that manufactures on a support.
- a discharge process in which the composition for forming a heat conductive layer is discharged toward the support, and For each position on the support, the first solvent weight loss time from when the heat conductive layer forming composition is discharged until the solid content concentration in the heat conductive layer forming composition reaches 90% by mass on the support is 10
- a method for producing a heat conductive layer which comprises a solvent weight loss step of reducing the amount of solvent in the heat conductive layer forming composition so as to take seconds or more. ⁇ 2> The first solvent weight loss time is 120 seconds or less. The method for producing a heat conductive layer according to ⁇ 1>.
- ⁇ 3> In the solvent weight loss step, at least one solvent weight loss treatment of depressurizing the atmosphere and heating the support is performed on the position on the support where the solid content concentration in the heat conductive layer forming composition exceeds 90% by mass.
- ⁇ 4> For each position on the support, the time from when the solid content concentration in the heat conductive layer forming composition exceeds 90% by mass on the support until the solvent weight loss treatment is started is 60 seconds or less.
- ⁇ 5> A second solvent weight loss from the solid content concentration in the heat conductive layer forming composition exceeding 90% by mass on the support to 99% by mass by further solvent weight loss for each position on the support.
- the time is 60-300 seconds
- ⁇ 6> A manufacturing method for producing a heat conductive layer having a thermal diffusivity of 3.0 ⁇ 10 -7 m 2 s -1 or more on a support using a heat conductive layer forming composition containing a resin, a filler and a solvent. , The application step of applying the composition for forming a heat conductive layer on a support by a spin coating method is included.
- a method for producing a heat-conducting layer in which a composition for forming a heat-conducting layer is supplied to a circular region having a radius of 10% of the length of the line segment. ⁇ 7> The support is rotated before the heat conductive layer forming composition is supplied to the circular region. The method for producing a heat conductive layer according to ⁇ 6>. ⁇ 8> In the above application step, the rotation speed of the support is changed.
- the method for producing a heat conductive layer according to ⁇ 6> or ⁇ 7>. ⁇ 9> In the above application step, the rotation direction of the support is clockwise. The method for producing a heat conductive layer according to any one of ⁇ 6> to ⁇ 8>. ⁇ 10> In the above application step, at the end of rotation of the support, the angular position of the support in the rotation direction is adjusted to the same angle position as at the start of rotation. The method for producing a heat conductive layer according to any one of ⁇ 6> to ⁇ 9>. ⁇ 11> The solid content concentration of the heat conductive layer forming composition before being supplied onto the support is less than 90% by mass. The application step includes a discharge step of discharging the heat conductive layer forming composition toward the support.
- the first solvent weight loss time from when the heat conductive layer forming composition is discharged until the solid content concentration in the heat conductive layer forming composition reaches 90% by mass on the support is 10 Rotate the support for more than a second,
- the average primary particle size of the filler is 10 ⁇ m or less.
- the content of the filler is 50 to 75% by volume based on the total solid content in the composition for forming a heat conductive layer.
- a method for producing a laminate including a support and a heat conductive layer which comprises producing a heat conductive layer on a support by the method for producing a heat conductive layer according to any one of ⁇ 1> to ⁇ 13>.
- a method for manufacturing a semiconductor device including a support and a heat conductive layer which comprises manufacturing the heat conductive layer on a support by the method for manufacturing a heat conductive layer according to any one of ⁇ 1> to ⁇ 13>.
- the thermal conductivity and electrical insulation of the heat conductive layer are appropriately exhibited.
- the numerical range represented by the symbol "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
- process means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
- the notation that does not describe substitutions and non-substituents means that those having no substituents as well as those having substituents are included.
- alkyl group when simply described as “alkyl group”, this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group).
- alkyl group when simply described as “alkyl group”, this means that it may be chain-like or cyclic, and in the case of chain-like, it may be linear or branched.
- exposure means not only drawing using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified.
- energy rays used for drawing include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, active rays such as extreme ultraviolet rays (EUV light) and X-rays, and particle beams such as electron beams and ion beams. Be done.
- (meth) acrylate means both “acrylate” and “methacrylate”, or either
- (meth) acrylic means both “acrylic” and “methacrylic", or , Either
- (meth) acryloyl means both “acryloyl” and “methacryloyl”, or either.
- the solid content in the composition means other components other than the solvent, and the content (concentration) of the solid content in the composition is, unless otherwise specified, based on the total mass of the composition. It is represented by the mass percentage of other components excluding the solvent.
- the temperature is 23 ° C. and the atmospheric pressure is 101325 Pa (1 atm).
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
- GPC measurement gel permeation chromatography
- Mw and Mn for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel are used as columns. It can be obtained by using Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
- the measurement is carried out using THF (tetrahydrofuran) as the eluent.
- a UV ray (ultraviolet) wavelength 254 nm detector is used for detection in GPC measurement.
- the method for producing a heat conductive layer of the present invention in the first aspect uses a composition for forming a heat conductive layer containing a resin, a filler and a solvent and having a solid content concentration of less than 90% by mass, and has a thermal diffusivity of 3.0.
- This is a manufacturing method for manufacturing a heat conductive layer having a size of ⁇ 10 -7 m 2 s -1 or more on a support.
- the method for manufacturing the heat conductive layer includes a discharge step of discharging the heat conductive layer forming composition toward the support, and forming the heat conductive layer after the heat conductive layer forming composition is discharged at each position on the support.
- the heat conductive layer so that the first solvent weight loss time until the solid content concentration in the composition for use reaches 90% by mass (hereinafter, also referred to as “first threshold concentration”) on the support is 10 seconds or more.
- a solvent weight loss step of reducing the amount of the solvent in the forming composition is included.
- the thermal conductivity and electrical insulation of the heat conductive layer are appropriately exhibited. The reason is not clear, but it is presumed to be as follows.
- a resin composition containing a filler such as the composition for forming a heat conductive layer used in the method for producing a heat conductive layer of the present invention, usually contains a filler dispersed in a dispersant. Therefore, if the filler is dispersed by the dispersant and the heat conductive layer forming composition is rapidly dried and solidified while the distance between the fillers remains large, the filler is fixed with a gap between the fillers. It ends up. If there is a gap between the fillers responsible for thermal conductivity, it is difficult to obtain sufficient thermal conductivity. Further, if the heat conductive layer forming composition dries and solidifies too quickly, only the surface dries and the solvent tends to remain in the gaps between the fillers.
- the first solvent weight loss time in the initial stage of drying which has a relatively low solid content concentration, is relatively long, such as 10 seconds or more, and in an environment where the filler easily moves (particularly, sedimentation), to some extent.
- the distance between the fillers can be shortened.
- improvement in thermal conductivity can be expected.
- rapid volatilization of the solvent can be suppressed, and only the surface can be prevented from drying and the solvent can be suppressed from remaining inside the coating film.
- the thermal conductivity and electrical insulation of the heat conductive layer are appropriately exhibited by the method for producing the heat conductive layer of the present invention.
- a composition for forming a heat conductive layer containing a resin, a filler and a solvent is used, and the thermal diffusivity is 3.0 ⁇ 10 -7 m 2 s -1.
- This is a manufacturing method for manufacturing the heat conductive layer as described above on the support.
- the method for producing the heat conductive layer includes an application step of applying the heat conductive layer forming composition on the support by a spin coating method, and when the heat conductive layer forming composition is supplied onto the support in the application step, A circular region whose radius is 10% of the length of a line segment centered on the application surface of the support and ending at the center of gravity and the point on the application surface farthest from the center of gravity.
- a circular region whose radius is 10% of the length of a line segment centered on the application surface of the support and ending at the center of gravity and the point on the application surface farthest from the center of gravity.
- the thermal conductivity and electrical insulation of the heat conductive layer are also appropriately exhibited by the method for producing the heat conductive layer of the present invention in the second aspect. The reason is not clear, but it is considered that the composition for forming the heat conductive layer was uniformly applied to the entire surface of the support.
- the method for producing a heat conductive layer of the present invention is a method for manufacturing a heat conductive layer having a thermal diffusivity of 3.0 ⁇ 10 -7 m 2 s -1 or more on a support. Since such a heat conductive layer has excellent thermal conductivity and electrical insulation, it can be suitably used as a heat dissipation resin insulating layer for semiconductor devices such as LSI devices.
- the heat conductive layer can be formed, for example, by applying a composition containing at least one kind of filler, a resin, and a solvent onto a substrate, and drying or curing the film.
- the heat conductive layer 4 of the present invention has a structure in which the filler 3 is dispersed in the resin film 2 formed on the base material 1.
- the heat conductive layer 4 exhibits high thermal conductivity because it contains the filler 3 and has a thermal diffusivity of 3.0 ⁇ 10 -7 m 2 s -1 or more. Therefore, the thermal energy E transmitted to the heat conductive layer 4 is rapidly released from the opposite side while transmitting the region where the filler 3 is present.
- the heat conductive layer may have a pattern shape depending on the semiconductor device to be applied.
- the thermal diffusivity of the heat conductive layer is preferably 3.0 ⁇ 10 -7 m 2 s -1 or more, and particularly preferably 1.0 ⁇ 10 -6 m 2 s -1 or more.
- the upper limit of the thermal diffusivity of the heat conductive layer is not particularly limited, but is practically 1.0 ⁇ 10 -4 m 2 s -1 or less.
- the volume resistivity of the heat conductive layer is preferably 1.0 ⁇ 10 11 ⁇ ⁇ cm or more, and particularly preferably 3.0 ⁇ 10 11 ⁇ ⁇ cm or more.
- the upper limit of the volume resistivity of the heat conductive layer is not particularly limited, but is practically 1.0 ⁇ 10 18 ⁇ ⁇ cm.
- composition for forming a heat conductive layer for forming the heat conductive layer will be described later.
- the discharge step is a step of supplying the heat conductive layer forming composition onto the support from a supply means such as a nozzle.
- the means for supplying the heat conductive layer forming composition is appropriately determined according to the method of applying the heat conductive layer forming composition to the support.
- a spin coating method As a method of applying the composition for forming a heat conductive layer, a spin coating method, a spray coating method, a slit coating method, a spiral coating method, a screen printing method, an inkjet method, a casting coating method, a roll coating method and a dropping method (drop casting).
- the spin coating method, the spray coating method and the slit coating method are preferable.
- the method for producing a heat conductive layer of the present invention is suitable for coating by a spin coating method.
- the support is not particularly limited and is appropriately selected according to the application.
- Examples of the support include a transparent substrate used for a liquid crystal display device and the like, and a semiconductor substrate used for a light emitting element, a solid-state image sensor, a semiconductor memory, a heat conductive sheet, a metal substrate, a substrate having metal wiring, a ceramics substrate, and the like.
- the transparent substrate is, for example, quartz glass, non-alkali glass, soda glass, borosilicate glass, aluminosilicate glass and the like. Other structures such as a transparent conductive film, a reflective film, and a protective film may be formed on these transparent substrates.
- the semiconductor substrate includes, for example, silicon, sapphire, silicon carbide, gallium nitride, aluminum, amorphous aluminum oxide, polycrystalline aluminum oxide, silicon nitride, silicon nitride, GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, etc. AlGa, InP, ZnO and the like.
- Other structures such as a PN junction layer, a light emitting layer, a photoelectric conversion layer, a complementary metal oxide semiconductor (CMOS) layer, and an electrode layer may be formed on these semiconductor substrates.
- CMOS complementary metal oxide semiconductor
- an undercoat layer may be provided on these supports in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface.
- the distance between the supply means (particularly the supply port) and the support when discharging the heat conductive layer forming composition is not particularly limited, and is appropriately selected according to the application method of the heat conductive layer forming composition.
- the distance is preferably 0.1 to 100 mm.
- the upper limit of the above numerical range is more preferably 50 mm or less, and further preferably 30 mm or less.
- the lower limit of the above numerical range is more preferably 1 mm or more, and further preferably 5 mm or more.
- the above distance is preferably 1 to 30 cm.
- the upper limit of the above numerical range is more preferably 20 cm or less, and further preferably 10 cm or less.
- the lower limit of the above numerical range is more preferably 2 cm or more, and further preferably 3 cm or more. In the case of the slit coating method, the distance is preferably 1 to 200 ⁇ m.
- the upper limit of the above numerical range is more preferably 150 ⁇ m or less, and further preferably 100 ⁇ m or less. Further, the lower limit of the above numerical range is more preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more.
- the position on the support for supplying the heat conductive layer forming composition is not particularly limited, but is appropriately set according to the method of applying the heat conductive layer forming composition.
- supplying the heat-conducting layer-forming composition to the circular region means that at least a part of the heat-conducting layer-forming composition discharged from the supply means is temporarily guided toward the circular region. Therefore, in the present invention, the case where the heat conductive layer forming composition only flows from the region outside the circular region to the circular region on the surface of the support is not included.
- the circular region for supplying the heat-conducting layer forming composition is a circular region having a radius of 8% of the length of the line segment among the circular regions centered on the center of gravity on the application surface. Is more preferable, and a circular region having a radius of 5% of the length of the line segment is further preferable.
- the support When supplying the composition for forming a heat conductive layer to the support, it is also preferable to rotate the support according to the application method (for example, spin coating method). Further, the support may be rotated after the heat conductive layer forming composition is supplied to the support. The specific rotation speed of the support will be described later.
- the application method for example, spin coating method
- the heat conductive layer forming composition supply means and the support is translated with respect to the other depending on the application method (for example, the slit coating method). It is preferable to scan the supply means of the heat conductive layer forming composition relative to the support.
- the scanning speed is preferably 0.1 to 50 cm / s.
- the upper limit of the above numerical range is more preferably 20 cm / s or less, and further preferably 10 cm / s or less. Further, the lower limit of the above numerical range is more preferably 0.5 cm / s or more, and further preferably 1.0 cm / s or more.
- the supply amount of the heat conductive layer forming composition is appropriately adjusted so that the coating film thickness and the dry film thickness of the heat conductive layer forming composition become desired values.
- the coating film thickness of the composition for forming a heat conductive layer is not particularly limited, and is appropriately adjusted depending on the intended use. When a composition containing a filler and a photopolymerization initiator is used, the coating film thickness is preferably 0.2 to 50 ⁇ m from the viewpoint of resolution and developability.
- the lower limit of this numerical range is more preferably 0.5 ⁇ m or more, and further preferably 1.0 ⁇ m or more. Further, the upper limit of this numerical value range is more preferably 35 ⁇ m or less, and further preferably 20 ⁇ m or less.
- the dry film thickness of the composition for forming a heat conductive layer is not particularly limited, and is appropriately adjusted depending on the intended use.
- the dry film thickness is preferably, for example, 0.1 to 50 ⁇ m.
- the lower limit of this numerical range is more preferably 0.2 ⁇ m or more, and further preferably 0.5 ⁇ m or more.
- the upper limit of this numerical range is more preferably 30 ⁇ m or less, and further preferably 15 ⁇ m or less from the viewpoint of thermal resistance.
- the solvent weight-loss step is a composition for forming a heat-conducting layer so that the first solvent weight-loss time is 10 seconds or more for each position on the support.
- This is a process of reducing the amount of solvent inside. That is, the solvent weight loss step can be said to be a step of controlling the time until the solid content concentration of the heat conductive layer forming composition having a solid content concentration of less than 90% by mass before supply reaches the first threshold concentration on the support. ..
- the thermal conductivity and electrical insulation of the heat conductive layer are appropriately exhibited.
- weight loss includes both reducing the amount of the solvent by separating it by volatilization or the like, and reducing the amount of the solvent and other components together by removing a part of the composition for forming a heat conductive layer. The meaning of is included.
- the start time of the first solvent weight loss time is when the heat conductive layer forming composition is discharged, that is, when the heat conductive layer forming composition is exposed to the outside air, as described above.
- the solid content concentration of the heat conductive layer forming composition is determined for each position on the support. For example, in the case of the spin coating method, since the heat conductive layer forming composition is rapidly deployed on the support, the solid content concentration of the heat conductive layer forming composition changes at the center of rotation and the outer edge of the support. There is almost no difference in the degree (however, even in the spin coating method, if the rotation speed is low or the application surface of the heat conductive layer forming composition is wide, the degree of change in the solid content concentration may differ. .).
- the position where the heat conductive layer forming composition is first supplied and the position where the heat conductive layer forming composition is finally supplied are different.
- the degree of change in the solid content concentration of the heat conductive layer forming composition tends to be different. Further, such a time difference problem becomes more remarkable when a large support such as a glass substrate for a flat panel display is used. Therefore, in order to form a high-quality and homogeneous heat-conducting layer on the support, the solid content concentration of the heat-conducting layer-forming composition should be determined for each position on the support in consideration of such a time difference. Is preferable.
- the solid content concentration of the composition for forming a heat conductive layer need to consider at least the region used as a product. That is, it is not necessary to satisfy the requirement of "first solvent weight loss time of 10 seconds or more" in a region that is cut and not used, such as the outer edge of the support.
- the solid content concentration of the heat conductive layer forming composition in the process of manufacturing the heat conductive layer is a calibration curve showing the relationship between the solid content concentration of the heat conductive layer forming composition and the execution time of the solvent weight reduction treatment, for example, the heat conductive layer. It can be prepared in advance for each formation composition and each type of solvent weight loss treatment, and can be estimated based on this calibration curve.
- the calibration curve can be created by, for example, the following method. After applying the composition for forming a heat conductive layer on the support, samples were prepared at regular intervals (for example, every 1 second, every 2 seconds, etc.) after the treatment during the process was stopped, and their masses were measured. , Obtain the measured value A.
- Specific combination methods include, for example, a method of rotating the support and then placing the support in a reduced pressure atmosphere, a method of heating the support after rotating the support, and a method of placing the support in a reduced pressure atmosphere.
- a method of heating the support a method of rotating the support in a reduced pressure atmosphere, a method of heating the support in a reduced pressure atmosphere, a method of rotating the support while heating, and a method of rotating the support while heating in a reduced pressure atmosphere.
- There is a way to rotate Among these methods, a method of rotating the support and then placing the support in a reduced pressure atmosphere, a method of heating the support after rotating the support, and a method of placing the support in a reduced pressure atmosphere and then supporting the support.
- a method of heating the body is preferable, a method of placing the support under a reduced pressure atmosphere after rotating the support, and a method of heating the support after rotating the support are more preferable.
- the time for maintaining the constant speed rotation of the support is preferably 1 to 300 seconds.
- the upper limit of the above numerical range is more preferably 180 seconds or less, and further preferably 60 seconds or less. Further, the lower limit of the above numerical range is more preferably 3 seconds or more, and may be 10 seconds or more.
- the rotation speed of the support is appropriately adjusted in the range of, for example, 50 to 6000 rpm.
- the upper limit of the above numerical range is more preferably 4000 rpm or less, and further preferably 3000 rpm or less.
- the lower limit of the above numerical range is more preferably 100 rpm or more, and further preferably 150 rpm or more.
- the rotation speed of the support may be appropriately changed from the initial rotation speed to the maximum rotation speed in a stepped shape or an inclined shape.
- the initial rotation speed is preferably, for example, 50 to 600 rpm.
- the upper limit of this numerical range is preferably 500 rpm or less, more preferably 450 rpm or less, and even more preferably 400 rpm or less.
- the lower limit of this numerical value range is preferably 100 rpm or more, more preferably 150 rpm or more, and further preferably 200 rpm or more.
- the maximum rotation speed is preferably 700 to 3000 rpm, for example.
- the upper limit of this numerical range is preferably 2700 rpm or less, more preferably 2400 rpm or less, and even more preferably 2200 rpm or less.
- the lower limit of this numerical value range is preferably 800 rpm or more, more preferably 850 rpm or more, and further preferably 900 rpm or more.
- the higher the rotation speed of the support the higher the rate of weight loss of the solvent (the amount of reduction of the solvent per unit time) in the composition for forming a heat conductive layer on the support.
- the heating temperature is preferably 50 to 150 ° C.
- the upper limit of the above numerical range is more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower.
- the lower limit of the above numerical range is more preferably 55 ° C. or higher, further preferably 60 ° C. or higher.
- the higher the heating temperature the higher the rate of weight loss of the solvent in the heat conductive layer forming composition on the support.
- the heating time is preferably 30 to 600 seconds.
- the upper limit of the above numerical range is more preferably 300 seconds or less, and further preferably 180 seconds or less.
- the lower limit of the above numerical range is more preferably 60 seconds or more, and further preferably 90 seconds or more.
- the temperature may be appropriately changed to, for example, a stepped shape or an inclined shape in the heat treatment.
- the lower limit of the first solvent weight loss time is preferably 11 seconds or longer, more preferably 15 seconds or longer, and may be 20 seconds or longer.
- the upper limit of the first solvent weight loss time is preferably 120 seconds or less, more preferably 100 seconds or less, and further preferably 80 seconds or less.
- the first adjustment of the solvent weight loss time includes the method of adjusting the solvent weight loss rate by changing the contents and conditions of the solvent weight loss treatment described above, as well as the initial supply of the heat conductive layer forming composition (that is, supply to the support). It can also be carried out by adjusting the solid content concentration itself in the above).
- the time from when the solid content concentration in the heat conductive layer forming composition exceeds the first threshold concentration on the support until the solvent weight loss treatment is started is 60 seconds or less. Is preferable. If both the decompression of the atmosphere and the heating of the support are performed after the solid content concentration exceeds the first threshold concentration, if either of the treatments is started within the above time. Often, both processes may have started within the above time. Thereby, the heat conductive layer can be formed more efficiently.
- the upper limit of the above numerical range is more preferably 40 seconds or less, further preferably 20 seconds or less, and may be 10 seconds or less.
- the time from when the solid content concentration in the heat conductive layer forming composition exceeds the first threshold concentration on the support until the solvent weight loss treatment is started is zero seconds, that is, the solvent weight loss such as heating and depressurization is performed. It is also possible that the solid content concentration in the heat conductive layer forming composition exceeds the first threshold concentration on the support during the treatment. In the above time from when the solid content concentration exceeds the first threshold concentration to when the solvent weight reduction treatment is started, the first decimal place and below are rounded up.
- the composition for forming the heat conductive layer is applied to the application surface of the support by the spin coating method, and the shape of the support is the center of gravity of the application surface of the support. Is useful when the shape does not coincide with the center of the circumscribed circle of the application surface.
- the composition for forming a heat conductive layer is applied to the surface of the support by the spin coating method because the support tends to be unstable with respect to rotation. It may be difficult to apply evenly.
- the heat conductive layer forming composition can be uniformly applied to the surface of the support by supplying the heat conductive layer forming composition to the predetermined circular region.
- the support having a predetermined shape as described above includes, for example, a circular substrate (wafer type substrate) having a straight portion (orientation flat) or a notch (notch) on the outer edge, or a rectangular substrate having a notch. (Panel type substrate) and the like.
- the size of the substrate is not particularly limited, but is preferably 25 to 125 cm.
- the upper limit of this numerical range may be 105 cm or less, or 65 cm or less. Further, the lower limit of this numerical range may be 30 cm or more, or 34 cm or more.
- the same material as the material described for the support in the first aspect can be used.
- the support it is preferable to rotate the support before the heat conductive layer forming composition is supplied to the circular region. As a result, the thermal conductivity and electrical insulation of the heat conductive layer are more appropriately exhibited.
- it is preferable to change the rotation speed of the support, and the rotation direction of the support may be counterclockwise, but is preferably clockwise. Further, in the application step, it is preferable to adjust the angular position of the support in the rotation direction to the same angle position as at the start of rotation at the end of rotation of the support. As a result, the support can be efficiently conveyed in the production line.
- the solid content concentration of the heat conductive layer forming composition before being supplied onto the support is less than 90% by mass
- the above-mentioned application step is a discharge step of discharging the heat conductive layer forming composition toward the support. Including, for each position on the support, from the time when the heat conductive layer forming composition is discharged until the solid content concentration in the heat conductive layer forming composition reaches 90% by mass (first threshold concentration) on the support. It is preferable to rotate the support so that the first solvent weight loss time is 10 seconds or more. As a result, the thermal conductivity and electrical insulation of the heat conductive layer are more appropriately exhibited.
- the first solvent weight loss time can be adjusted by adjusting the rotation speed and the rotation time of the support as described in the method for manufacturing the heat conductive layer according to the first aspect. Further, when adjusting the first solvent weight loss time, at least one treatment of decompression treatment of the atmosphere and heat treatment of the support may be combined with the rotation of the support. Such a combination method is the same as the combination method described in the method for producing the heat conductive layer of the first aspect.
- the method for producing a heat conductive layer of the present invention preferably includes a step of exposing the dry film after forming the dry film by the steps such as the discharge step and the solvent weight reduction step described above.
- the method for producing a heat conductive layer of the present invention may further include a step of forming a pattern on the dry film.
- the heat conductive layer is used as a flat film, it is not necessary to perform the step of forming a pattern on the dry film.
- the composition for forming a heat conductive layer preferably contains a photopolymerization initiator and a polymerizable compound. Further, the resin preferably contains an alkali-soluble resin.
- the steps of forming a pattern include a step of exposing a dry film formed on a substrate in a pattern (exposure step) and a step of developing and removing a non-exposed portion or an exposed portion to form a pattern (development step). , Is preferably included. As a result, a heat conductive layer having a pattern shape is formed.
- a dry film on a base material can be exposed to a pattern using an exposure device such as a stepper through a mask having a predetermined mask pattern. Thereby, for example, the exposed portion can be cured.
- Irradiation dose exposure dose
- Exposure dose for example, preferably from 0.03 ⁇ 2.5J / cm 2, and more preferably 0.05 ⁇ 1.0J / cm 2.
- the oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere where the oxygen concentration is 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free). ), Or in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume).
- the exposure illuminance can be appropriately set and can be normally selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15,000 W / m 2 , 35,000 W / m 2). ..
- Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
- the unexposed portion is developed and removed to form a pattern.
- Development and removal of the non-exposed area can be performed using a developing solution.
- the developer may be either an alkaline developer or an organic solvent.
- the temperature of the developer is preferably, for example, 20 to 30 ° C.
- the development time is preferably 20 to 180 seconds, more preferably 20 to 90 seconds.
- heating and / or exposure may be further performed.
- the curing of the film can be further advanced to produce a more firmly cured film.
- the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 500 ° C., more preferably 80 to 450 ° C., further preferably 140 to 400 ° C., and even more preferably 160 to 350 ° C.
- the heat conductive layer contains a polyimide precursor
- the cyclization reaction of the polyimide precursor proceeds in this heating step.
- the film thickness of the heat conductive layer after exposure obtained by the above-mentioned production method of the present invention is preferably 0.2 to 50 ⁇ m.
- the lower limit is more preferably 0.5 ⁇ m or more, and further preferably 1.0 ⁇ m or more.
- the upper limit is more preferably 40 ⁇ m or less, and further preferably 30 ⁇ m or less.
- FIG. 2 is a time chart showing the time relationship between the solid content concentration and the solvent weight reduction treatment at a predetermined position on the support.
- the composition for forming a heat conductive layer is applied onto the support by the spin coating method.
- the scale of the time chart in the figure is changed as appropriate for convenience, and does not necessarily match the actual time axis.
- the meanings of the symbols in FIG. 2 are as follows.
- -Solid line A Solid content concentration of the composition for forming a heat conductive layer.
- -Concentration C 1 First threshold concentration (90% by mass)
- C 2 Second threshold concentration (99% by mass)
- -Step ST 1 The step until the solid content concentration of the heat conductive layer forming composition reaches the first threshold concentration (first step).
- -Step ST 2 A step after the solid content concentration of the heat conductive layer forming composition reaches the first threshold concentration (second step).
- Dashed line B Rotational speed of the rotating stage.
- time t a rotation start time of the rotary stage.
- time t b Rotation end time of the rotation stage.
- -Hatching area D Implementation period of solvent weight reduction treatment (heating) in the second stage.
- -Time t d The start time of the solvent weight loss treatment in the second stage.
- -Time t 1 The time at which the heat conductive layer forming composition is discharged onto the wafer.
- -Time t 2 The time when the solid content concentration of the heat conductive layer forming composition reached the first threshold concentration.
- -Time t 3 The time when the solid content concentration of the heat conductive layer forming composition reached the second threshold concentration.
- an initial rotational speed e.g. 300 rpm
- a maximum rotational speed e.g. 1000 rpm
- the heat conductive layer forming composition is discharged from the nozzle of the spin coater toward the support, and the heat conductive layer forming composition is supplied onto the support.
- the solid concentration of the heat-conducting layer forming composition is less than C 1.
- the first solvent weight loss time is T 1 in the figure.
- the rotation of the support by the rotation stage corresponds to the solvent weight loss treatment in the first stage, and for example, by adjusting the supply timing, rotation speed, rotation time, etc. of the heat conductive layer forming composition.
- the solvent weight loss rate can be adjusted.
- the first solvent loss time T 1 of the present invention can be adjusted with the adjustment of such solvents weight loss rate, by adjusting the solid concentration of the heat-conducting layer forming composition prior to delivery.
- the heat treatment is started.
- this heat treatment of the support by the rotating stage corresponds to the solvent weight loss treatment in the second stage, and the heating temperature can be adjusted to adjust the solvent weight loss rate.
- the second solvent weight loss time is T 3 in the figure.
- the heat-conducting layer-forming composition is dried until the film thickness of the supplied heat-conducting layer-forming composition becomes sufficiently stable, and then the heat treatment is completed. This completes the application of the heat conductive layer forming composition to the support.
- FIG. 4 is a time chart showing the time relationship between the solid content concentration and the solvent weight reduction treatment at a predetermined position on the support.
- the composition for forming a heat conductive layer is applied onto the support by the spray coating method.
- the meanings of the new reference numerals in FIG. 4 are as follows. Further, among the reference numerals in FIG. 4, those common to the reference numerals in FIG. 2 are synonymous with the reference numerals in FIG. 2.
- -Hatching area D 1 Implementation period of solvent weight reduction treatment (decompression).
- -Hatching area D 2 Implementation period of solvent weight reduction treatment (heating).
- the atmosphere inside the processing space of the spray coater is reduced to, for example, 100 Pa (region D 1 ).
- the atmosphere inside the processing space is returned to the atmosphere.
- the first solvent weight loss time is T 1 in the figure.
- the operation of returning the atmosphere to the atmosphere may be performed before the solid content concentration reaches the first threshold concentration or after the solid content concentration reaches the first threshold concentration.
- the decompression of the atmosphere inside the treatment space corresponds to the solvent weight loss treatment in the first stage, and the solvent weight loss rate can be adjusted by adjusting the decompression degree of the atmosphere.
- the heat treatment by the fixed stage is started.
- this heat treatment of the support by the fixed stage corresponds to the solvent weight loss treatment in the second stage, and the heating temperature can be adjusted to adjust the solvent weight loss rate.
- the second solvent weight loss time is T 3 in the figure.
- the heat-conducting layer-forming composition is dried until the film thickness of the supplied heat-conducting layer-forming composition becomes sufficiently stable, and then the heat treatment is completed. This completes the application of the heat conductive layer forming composition to the support.
- embodiment 2 in the period represented by the region D 1 of the in Figure 4, in place of the solvent weight loss treatment by pressure reduction, employs a solvent reduction treatment by heating, expressed in regions D 2 in FIG. 4 In the period, the solvent weight loss treatment by decompression may be adopted instead of the solvent weight loss treatment by heating.
- FIG. 5 is a time chart showing the time relationship between the solid content concentration and the solvent weight reduction treatment at a predetermined position on the support.
- the composition for forming a heat conductive layer is applied onto the support in a reduced pressure atmosphere by the slit coating method, and further heat treatment is carried out in the second step.
- symbols in FIG. 5 those common to the symbols in FIG. 2 have the same meaning as the symbols in FIG. 2, and those common to the symbols in FIG. 4 are the symbols in FIG. It is synonymous with meaning.
- the atmosphere inside the processing space of the slit coater is reduced to, for example, 100 Pa (region D 1 ), and this reduced pressure state is maintained almost throughout the application process of the heat conductive layer forming composition.
- the first solvent weight loss time is T 1 in the figure.
- the decompression of the atmosphere inside the treatment space corresponds to the solvent weight loss treatment in the first stage, and the solvent weight loss rate can be adjusted by adjusting the decompression degree of the atmosphere.
- concentration C C 2
- the second solvent weight loss time is T 3 in the figure.
- the heat-conducting layer-forming composition is dried until the film thickness of the supplied heat-conducting layer-forming composition is sufficiently stabilized, and then the atmosphere is returned to the atmosphere and the heat treatment is completed. This completes the application of the heat conductive layer forming composition to the support.
- embodiment 3 in the period represented by the region D 1 of the in Figure 5, in place of the solvent weight loss treatment by pressure reduction, employs a solvent reduction treatment by heating, expressed in regions D 2 in FIG. 5 In the period, the solvent weight loss treatment by decompression may be adopted instead of the solvent weight loss treatment by heating.
- composition for forming a heat conductive layer ⁇ Composition for forming a heat conductive layer>
- each component of the composition for forming a heat conductive layer will be described.
- the composition of the present invention contains a filler.
- the filler is preferably thermally conductive.
- the filler may be electrically insulating, semiconductor or conductive.
- the degree of electrical insulation and conductivity is appropriately selected depending on the design and purpose.
- the lower limit of the volume resistivity of the filler is preferably 1.0 ⁇ 10 11 ⁇ ⁇ cm or more, and 3.0 ⁇ 10 11 ⁇ ⁇ cm or more. Is more preferable, and 1.0 ⁇ 10 12 ⁇ ⁇ cm or more is particularly preferable.
- the upper limit of the volume resistivity is not particularly limited, but is practically 1.0 ⁇ 10 18 ⁇ ⁇ cm.
- the lower limit of the volume resistivity of the filler is not particularly limited, but is practically 1.0 ⁇ 10 -7 ⁇ ⁇ cm or more. Further, the upper limit of the volume resistivity is preferably less than 1.0 ⁇ 10 11 ⁇ ⁇ cm.
- the thermal diffusivity of the filler is, for example, 1.0 ⁇ 10 -6 m 2 s -1 or more, preferably 2.0 ⁇ 10 -6 m 2 s -1 or more, preferably 3.0 ⁇ 10 ⁇ . It is particularly preferable that it is 6 m 2 s -1 or more.
- the upper limit of the thermal diffusivity of the filler is not particularly limited, but is practically 1.0 ⁇ 10 -4 m 2 s -1 or less.
- the density of the filler is, for example, 4.0 g / cm 3 or less, and more preferably 3.0 g / cm 3 or less.
- the lower limit of the filler density is not particularly limited, but is practically 1.0 g / cm 3 or less.
- the density of the filler in the present specification means the density of the solid content among the components constituting the filler. To do.
- the filler contains an electrically insulating material.
- the electrically insulating filler material is, for example, an electrically insulating ceramic composed of a nitrogen compound, an oxygen compound, a silicon compound, a boron compound, a carbon compound, and a composite compound thereof.
- the nitrogen compound include boron nitride, aluminum nitride, silicon nitride and the like.
- the oxygen compound include metal oxides such as aluminum oxide (alumina), magnesium oxide (magnesia), zinc oxide, silicon oxide (silica), beryllium oxide, titanium oxide (titania), copper oxide, and cuprous oxide.
- Examples of the silicon compound and the carbon compound include silicon carbide.
- Examples of the boron compound include metal borides such as titanium boring.
- carbon compounds include, for example, diamond, which is a carbon substrate material in which ⁇ bonds are dominant.
- examples of the above-mentioned complex compound include mineral ceramics such as magnesite (magnesium carbonate), perobskite (calcium titanate), talc, mica, kaolin, bentonite, and pyroferrite.
- the electrically insulating filler material may be a metal hydroxide such as magnesium hydroxide or aluminum hydroxide.
- the filler material preferably contains at least one of ceramics made of nitrogen compounds, ceramics made of metal oxides and metal hydroxides.
- the filler material preferably contains, for example, at least one of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide, beryllium oxide and aluminum hydroxide.
- the filler material is particularly preferably at least one of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, zinc oxide and beryllium oxide, and of boron nitride, aluminum nitride, silicon nitride and aluminum oxide.
- Boron nitride includes c-BN (cubic structure), w-BN (Ults ore structure), h-BN (hexagonal structure), r-BN (diamond crystal structure), and t-BN (random layer structure). ) Etc. may be any structure. Boron nitride has a spherical shape and a scaly shape, and any of them can be used.
- the conductive filler material examples include graphite, carbon black, graphite, carbon fibers (pitch type, PAN type), carbon nanotubes (CNT), carbon nanofibers (CNF), and other carbon substrate materials in which ⁇ bonds are dominant. Can be mentioned. Further, as such a filler material, a metal such as silver, copper, iron, nickel, aluminum and titanium, and an alloy such as stainless steel (SUS) may be used. Further, as such a filler material, a conductive metal oxide such as zinc oxide doped with a different element or a conductive ceramic such as ferrite can also be used.
- the filler may have a structure in which semiconductors or conductive thermally conductive particles are coated or surface-treated with an electrically insulating material such as silica.
- an electrically insulating material such as silica.
- the thermal conductivity and the electrical insulation can be easily controlled individually, so that the thermal conductivity and the electrical insulation can be easily adjusted.
- a method of forming a silica film on the surface a water glass method and a sol-gel method can be mentioned.
- fillers can be used alone or in combination of two or more.
- shape of the filler various shapes can be used, and examples thereof include a fibrous shape, a plate shape, a scale shape, a rod shape, a spherical shape, a tube shape, a curved plate shape, and a needle shape.
- the average primary particle size of the filler is preferably 0.01 to 30 ⁇ m.
- the lower limit is more preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and particularly preferably 0.3 ⁇ m or more.
- the upper limit is more preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
- the "average primary particle size" of the filler can be determined by observing the filler in the dispersion liquid with a transmission electron microscope (TEM) and observing a portion (primary particles) in which the filler particles are not aggregated.
- TEM transmission electron microscope
- the primary particles of the filler are photographed by a transmission electron microscope using a transmission electron microscope, and then image processing is performed using the photograph with an image processing apparatus to measure the particle size distribution of the filler. Then, the arithmetic mean diameter based on the number calculated from the particle size distribution is adopted as the "average primary particle diameter" of the filler.
- an electron microscope (H-7000) manufactured by Hitachi, Ltd. is used as a transmission electron microscope
- a Luzex AP manufactured by Nireco Corporation is used as an image processing apparatus.
- the filler may contain a granular mixture in which at least two kinds of particle groups having different average primary particle diameters are mixed.
- the "average primary particle size" of a certain particle group is also obtained by the same method as in the case of the "average primary particle size” of the filler.
- small particles are buried between large particles, and the distance between the fillers is reduced and the contact points are further reduced as compared with the case where only a single diameter filler is contained.
- thermal conductivity improves.
- two kinds of particle groups having different average primary particle diameters are mixed, two peaks are observed in the particle size distribution of the filler containing these particle groups. Therefore, by confirming the number of peaks in the particle size distribution of the filler, it is possible to confirm how many kinds of particle groups having different average primary particle diameters are contained in the granular mixture which is the filler.
- the content of the filler in the composition is preferably 1% by volume or more, more preferably 10% by volume or more, and more preferably 20% by volume or more, based on the volume of the total solid content of this composition. It is particularly preferable, and it is most preferable that it is 50% by volume or more. Further, from the viewpoint of processability by lithography, it is more preferably 85% by volume or less, further preferably 81% by volume or less, and 75% by volume or less with respect to the volume of the total solid content of the composition. Is most preferable.
- the content of the filler in the composition is preferably 10% by mass or more, more preferably 30% by mass or more, based on the mass of the total solid content of this composition.
- the upper limit of this ratio is preferably 90% by mass or less, and particularly preferably 75% by mass or less, from the viewpoint of processability by lithography. In this way, by considering processability in addition to thermal conductivity and electrical insulation, a heat conductive layer having high thermal conductivity and electrical insulation can be formed at a desired position and pattern.
- the content of the filler with respect to the volume of the total solid content of the composition is calculated as the ratio of the volume of the filler to the volume of the heat guide layer in the heat guide layer after the solvent weight loss step. The calculation of each volume is performed under the condition of 23 ° C.
- the proportion of the particle group having an average primary particle diameter of 0.5 to 15 ⁇ m in the filler is preferably 50% by mass or more, more preferably 80% by mass or more.
- the upper limit of this ratio can be 100% by mass or 99% by mass or less. From the viewpoint of processability by lithography, this ratio is preferably 99% by mass or less, and more preferably 95% by mass or less.
- one type or a combination of two or more types of fillers can be used, and when two or more types of fillers are contained, it is preferable that the total amount thereof is within the above range.
- the resin used in the production of the heat conductive layer of the present invention is used, for example, in a binder used for bonding fillers, a dispersant used for dispersing fillers in a composition, and used for forming an insulating layer. It may contain a polymerizable compound to be used, a polymerization accelerator used for accelerating the polymerization reaction of the polymerizable compound, and the like. However, such an application of the resin is an example, and it can be used for a purpose other than such an application.
- the resin preferably contains at least one of a polyimide resin, an acrylic resin, and an epoxy resin. Hereinafter, the resin will be described in detail.
- the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
- the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
- the lower limit is preferably 3,000 or more, and more preferably 5,000 or more.
- the resin used for the heat conductive layer of the present invention preferably contains a binder.
- a binder By containing the binder, the film properties such as the strength of the film are improved.
- Any known binder can be used. Examples of such a resin include radical polymers having a carboxyl group in the side chain, for example, JP-A-59-044615, JP-A-54-034327, JP-A-58-012577, and JP-A-54-02595.
- the resins described in JP-A, JP-A-54-092733, JP-A-59-053836, and JP-A-59-071048 can be used.
- such a resin is a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, homopolymerizing or copolymerizing a monomer having an acid anhydride, and hydrolyzing or half-esterifying or halving the acid anhydride unit.
- An amidated resin an epoxy resin obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride, or the like.
- the monomer having a carboxyl group examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like, and examples of the monomer having an acid anhydride include maleic anhydride and the like. Be done.
- the alkali-soluble resin may be an acidic cellulose derivative having a carboxyl group in the side chain, or a polymer in which a cyclic acid anhydride is added to a polymer having a hydroxyl group.
- a known resin can be appropriately used.
- paragraphs [0055] to [0191] of U.S. Patent Application Publication No. 2016/0274458, paragraphs [0035] to [0085] of U.S. Patent Application Publication No. 2015/0004544, U.S. Patent Application Publication No. 2016. / 0147150 The known resin disclosed in paragraphs [0045] to [0090] of the specification can be preferably used as the resin (A). These contents are incorporated in the present specification.
- the acid-degradable group preferably has a structure in which a polar group is protected by a group (leaving group) that is decomposed and eliminated by the action of an acid.
- Polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imide groups.
- the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than the hydroxyl group directly bonded on the aromatic ring (phenolic hydroxyl group), and the ⁇ -position of the hydroxyl group is electron attraction such as a fluorine atom. Excludes aliphatic alcohols substituted with sex groups (eg, hexafluoroisopropanol groups, etc.).
- the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
- Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
- the resin (A) preferably has the repeating unit described in paragraphs [0336] to [0369] of U.S. Patent Application Publication No. 2016/0070167 as the repeating unit having an acid-degradable group, and the contents thereof include. Incorporated herein.
- the resin (A) is decomposed by the action of an acid described in paragraphs [0363] to [0364] of US Patent Application Publication No. 2016/0070167 as a repeating unit having an acid-degradable group to form an alcohol. It may have a repeating unit containing a group that produces a sex hydroxyl group, the contents of which are incorporated herein.
- the resin (A) may contain a repeating unit having an acid-decomposable group alone or in combination of two or more.
- the content of the repeating unit having an acid-degradable group contained in the resin (A) (the total of a plurality of repeating units having an acid-degradable group) is determined with respect to all the repeating units of the resin (A). 10 to 90 mol% is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is further preferable.
- the resin (A) preferably has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.
- the resin (A) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, as a repeating unit of US Patent Application Publication No. 2016/0070167, paragraphs [0370] to [0414]. ] It is also preferable to have the repeating unit described in the above, and this content is incorporated in the present specification.
- the resin (A) may contain a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may contain two or more of them in combination.
- the content of the repeating unit having at least one selected from the group consisting of the lactone structure, the sultone structure, and the carbonate structure contained in the resin (A) (selected from the group consisting of the lactone structure, the sultone structure, and the carbonate structure). If there are a plurality of repeating units having at least one type, the total) is preferably 5 to 70 mol%, preferably 10 to 65 mol%, based on all the repeating units of the resin (A). More preferably, it is 20 to 60 mol%.
- the resin (A) preferably has a repeating unit having a polar group.
- the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group.
- the repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Moreover, it is preferable that the repeating unit having a polar group does not have an acid-degradable group.
- the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornane group.
- the content of the repeating unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol%, based on all the repeating units in the resin (A).
- the resin (A) may contain a repeating unit having a polar group alone or in combination of two or more.
- the resin (A) contains two or more types of repeating units having polar groups, it is preferable that the total amount thereof is within the above numerical range.
- the resin (A) can further have a repeating unit that has neither an acid-degradable group nor a polar group.
- the repeating unit having neither an acid-degradable group nor a polar group preferably has an alicyclic hydrocarbon structure. Examples of the repeating unit having neither an acid-degradable group nor a polar group include the repeating units described in paragraphs [0236] to [0237] of US Patent Application Publication No. 2016/0026083. This content is incorporated herein.
- repeating unit having neither an acid-degradable group nor a polar group the repeating unit disclosed in paragraph [0433] of US Patent Application Publication No. 2016/0070167 can be mentioned. This may be incorporated herein by reference.
- the content of the repeating unit having neither an acid-degradable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on all the repeating units in the resin (A). More preferably, it is 5 to 25 mol%.
- the resin (A) may contain a repeating unit having neither an acid-decomposable group nor a polar group alone or in combination of two or more. When the resin (A) contains two or more such repeating units, it is preferable that the total amount thereof is in the above numerical range.
- the resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics of resist such as resolution, heat resistance, and sensitivity. It is possible to have various repeating structural units for the purpose of Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a monomer.
- Examples of the monomer include compounds having one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. Can be mentioned.
- the molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.
- the resin used for the heat conductive layer of the present invention preferably contains a resin soluble in an alkaline developer.
- the alkali-soluble resin may be a linear organic polymer, and is a group that promotes at least one alkali dissolution in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). Can be appropriately selected from the polymers having.
- the same resin may act as a binder and an alkali-soluble resin.
- the weight average molecular weight (Mw) of the alkali-soluble resin is not particularly limited, and is preferably 5000 to 200,000.
- the upper limit is preferably 100,000 or less, and more preferably 20,000 or less.
- the number average molecular weight (Mn) of the alkali-soluble resin is preferably 1,000 to 20,000.
- the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
- the lower limit is more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more.
- the upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.
- the alkali-soluble resin is preferably a polymer having a carboxyl group in the side chain, and is preferably a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified malein.
- examples thereof include acid copolymers, alkali-soluble phenol resins such as novolak type resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group to which an acid anhydride is added.
- a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
- examples of other monomers copolymerizable with (meth) acrylic acid include the monomers described in paragraphs 0017 to 0019 of Japanese Patent Application Laid-Open No. 2015-034961. Examples thereof include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds, and N-substituted maleimide monomers.
- alkyl (meth) acrylate and aryl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate.
- Examples of the vinyl compound include styrene, ⁇ -methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like.
- Examples of the N-substituted maleimide monomer include N-phenylmaleimide and N-cyclohexylmaleimide described in JP-A-10-300922.
- the other monomers copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.
- Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth). It is preferably a multiple copolymer composed of acrylate / (meth) acrylic acid / other monomer. Further, the alkali-soluble resin may be a copolymer of 2-hydroxyethyl (meth) acrylate.
- the alkali-soluble resin is a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and 2-hydroxy-3-phenoxypropyl acrylate described in JP-A-07-140654.
- Diamond Shamlock Co., Ltd. shows Diamond Shamlock Co., Ltd.
- Viscort R-264 shows KS resist 106.
- Cyclomer P series for example, ACA230AA
- Praxel CF200 series all manufactured by Daicel Co., Ltd.
- Ebeclyl3800 manufactured by Daicel UCB Co., Ltd.
- Acrylic RD -F8 manufactured by Nippon Catalyst Co., Ltd.
- the resin used for the heat conductive layer of the present invention can contain a dispersant.
- Dispersants include, for example, amine group resins (polyamide amines and salts thereof, etc.), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates. , (Meta) acrylic copolymer, naphthalene sulfonate formarin condensate and the like.
- the dispersant preferably has a site having an adsorptive ability to the filler (hereinafter referred to as "adsorption site").
- the adsorption sites include an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxyl group and a sulfonamide. Examples thereof include a monovalent substituent having at least one selected from the group consisting of a group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group.
- the adsorption site is preferably an acid-based adsorption site.
- the acid-based adsorption site include acid groups. Among them, it is preferable that the acid-based adsorption site is at least one of a phosphorus atom-containing group and a carboxyl group.
- the phosphorus atom-containing group include a phosphoric acid ester group, a polyphosphoric acid ester group, and a phosphoric acid group.
- the dispersant is preferably a resin represented by the following formula (1).
- R 1 represents a (m + n) -valent linking group
- R 2 represents a single bond or a divalent linking group
- a 1 is an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxyl group, and a sulfonamide group.
- n A 1 and R 2 may be the same or different, respectively.
- m represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies an integer of 3 to 10.
- P 1 represents a monovalent polymer chain.
- the m P 1s may be the same or different.
- the substituent A 1 of the resin represented by the formula (1) can interact with a filler (for example, inorganic particles such as titanium oxide). Therefore, the resin represented by the formula (1) has n (1 to 9) substituents A 1 and thus strongly interacts with the filler to improve the dispersibility of the filler in the composition. it can. Further, in the resin represented by the formula (1), since the polymer chain P 1 having m pieces can function as a steric repulsive group, having m pieces exerts a good steric repulsive force and makes the filler uniform. Can be dispersed in. For details of the monovalent substituent represented by A 1 , paragraphs 0041 to 0070 of JP-A-2007-277514 can be referred to, and the contents thereof are incorporated in the present specification.
- R 1 represents a (m + n) valent linking group.
- the (m + n) -valent linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and It contains a group consisting of 0 to 20 sulfur atoms.
- the (m + n) valent linking group is, for example, a group composed of the following structural units or a combination of two or more of the following structural units (may form a ring structure).
- paragraphs 0076 to 0084 of JP-A-2007-277514 can be referred to, and the contents thereof are incorporated in the present specification.
- P 1 represents a monovalent polymer chain.
- the monovalent polymer chain is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound.
- paragraphs 0087 to 098 of JP-A-2007-277514 can be referred to, and the contents thereof are incorporated in the present specification.
- Examples of the polymer dispersant represented by the above formula (1) include the description in paragraph 0039 of JP-A-2007-277514 (corresponding US Patent Application Publication No. 2010/0233595 ⁇ 0053>) and The descriptions in paragraphs 0081 to 0117 of JP-A-2015-034961 can be referred to, and these contents are incorporated in the present specification.
- a graft copolymer containing a repeating unit represented by any of the following formulas (11) to (14) can also be used.
- W 1 , W 2 , W 3 , and W 4 independently represent an oxygen atom or NH
- X 1 , X 2 , X 3 , X 4 , and X respectively.
- 5 each independently represents a hydrogen atom or a monovalent organic group
- Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group
- Z 1 , Z 2 , Z 3 and Z 4 independently represents a monovalent organic group
- R 3 represents an alkylene group
- R 4 represents a hydrogen atom or a monovalent organic group
- n, m, p, and q each independently represent 1 to 1 to q.
- W 1 , W 2 , W 3 and W 4 are preferably oxygen atoms.
- X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a hydrogen atom or a methyl group. Methyl groups are particularly preferred.
- Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group, and the linking group is not particularly structurally restricted.
- the structure of the monovalent organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 is not particularly limited, and specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, Examples thereof include an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group.
- the organic groups represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are preferable from the viewpoint of improving dispersibility, and each of them has 5 to 24 carbon atoms independently.
- Alkyl group or alkoxy group is preferable.
- a branched alkyl group having 5 to 24 carbon atoms, a cycloalkyl group having 5 to 24 carbon atoms, and carbon are independently used.
- Alkoxy groups of numbers 5 to 24 are particularly preferred.
- the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
- J and k in the formulas (11) and (12) are preferably integers of 4 to 6 and most preferably 5 from the viewpoint of dispersion stability and developability.
- R 3 is preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. when p is 2 ⁇ 500, R 3 existing in plural numbers may be different from one another the same.
- the monovalent organic group of R 4 is not particularly structurally limited.
- Preferred examples of R 4 include a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
- R 4 is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 5 to 20 carbon atoms are preferable, and 1 to 20 carbon atoms are preferable.
- the linear alkyl group of 1 to 6 is more preferable, and the linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
- q is 2 to 500
- a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
- the graft copolymer is, for example, a resin having the following structure. Further, the graft copolymer is, for example, a resin described in paragraphs 0072 to 0094 of JP2012-255128A, and the contents thereof are incorporated in the present specification.
- the dispersant is also preferably an oligoimine-based dispersant containing a basic nitrogen atom in at least one of the main chain and the side chain.
- the oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less, an oligomer chain having 40 to 10,000 atoms, or a side chain containing a polymer chain Y, and has a main chain and a side chain.
- a resin having a basic nitrogen atom in at least one of the side chains is preferable.
- This resin interacts with a filler (for example, inorganic particles such as titanium oxide) with both a nitrogen atom and a functional group having a pKa14 or less of the partial structure X, and the dispersant has 40 to 10,000 atoms.
- a filler for example, inorganic particles such as titanium oxide
- the oligomer chain or the polymer chain Y functions as a steric repulsive group, so that good dispersibility can be exhibited and the filler can be uniformly dispersed. Further, the precipitation of the filler can be suppressed for a long period of time by the interaction between the oligomer chain or the polymer chain Y and the solvent. Further, since the oligomer chain or the polymer chain Y functions as a steric repulsive group, aggregation of the filler is prevented, so that excellent dispersibility can be obtained even if the content of the filler is increased.
- the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity, but it is preferable that the resin contains a structure having a nitrogen atom of pKb14 or less, and a structure having a nitrogen atom of pKb10 or less. Is more preferable.
- pKb base strength refers to pKb at a water temperature of 25 ° C., is one of the indexes for quantitatively expressing the strength of a base, and is synonymous with a basicity constant.
- the functional group having pKa14 or less contained in the partial structure X is not particularly limited, and the structure or the like is not particularly limited as long as the physical properties satisfy this condition.
- a functional group having a pKa of 12 or less is preferable, and a functional group having a pKa of 11 or less is most preferable.
- a carboxyl group pKa about 3 to 5
- a sulfo group pKa about -3 to -2
- a -COCH 2 CO- group pKa about 8 to 10
- a -COCH 2 CN group pKa
- the partial structure X having a functional group of pKa14 or less is preferably directly bonded to a basic nitrogen atom in a repeating unit containing a nitrogen atom.
- the basic nitrogen atom of the repeating unit containing the basic nitrogen atom and the partial structure X may be linked not only by a covalent bond but also by an ionic bond to form a salt.
- the oligoimine-based dispersant has a repeating unit containing a basic nitrogen atom to which a partial structure X having a functional group of pKa14 or less is bonded, and an oligomer chain or a polymer chain Y having 40 to 10,000 atoms in the side chain. It is preferably a resin.
- the repeating unit is a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydialylamine-based repeating unit, a metaxylene diamine-epichlorohydrin polycondensate-based repeating unit, and the like.
- the lower term in poly (lower alkyleneimine) means that the carbon number is 1 to 5, and the lower alkyleneimine means the alkyleneimine having 1 to 5 carbon atoms.
- Examples of the oligomer chain or polymer chain Y having 40 to 10,000 atoms include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylic acid ester that can be linked to the main chain portion of the dispersant.
- the binding site of the oligomer chain or the polymer chain Y to the resin is preferably the end of the oligomer chain or the polymer chain Y.
- Oligomer chain or polymer chain Y is selected from poly (lower alkyleneimine) -based repeating unit, polyallylamine-based repeating unit, polydialylamine-based repeating unit, metaxylene diamine-epichlorohydrin polycondensation-based repeating unit, and polyvinylamine-based repeating unit. It is preferably bonded to a nitrogen atom in at least one repeating unit.
- the bonding mode between the oligomer chain or the polymer chain Y and the main chain portion having the repeating unit as described above is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond.
- the oligomer chain or polymer chain Y preferably has an amide bond or an ionic bond as a carboxylate with a nitrogen atom in a repeating unit containing a nitrogen atom.
- the number of atoms of the oligomer chain or the polymer chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoint of dispersibility, dispersion stability and developability. Further, the number average molecular weight of the oligomer chain or the polymer chain Y can be measured by the polystyrene conversion value by the GPC method. The number average molecular weight of the oligomer chain or the polymer chain Y is preferably 1,000 to 50,000, more preferably 1,000 to 30,000.
- the oligoimine-based dispersant is, for example, at least one of a repeating unit represented by the formula (I-1), a repeating unit represented by the formula (I-2), and a repeating unit represented by the formula (I-2a). It is a resin containing seeds.
- R 1 and R 2 independently represent a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a independently represents an integer of 1 to 5. In the present specification, * (asterisk) represents a connecting portion between repeating units. R 8 and R 9 are independently synonymous with R 1.
- L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), and a heteroarylene group (preferably having 1 to 6 carbon atoms).
- R 6 is preferable), an imino group (preferably having 0 to 6 carbon atoms), an ether group, a thioether group, a carbonyl group, and a linking group according to a combination thereof.
- a single bond or a -CR 5 R 6 -NR 7 - it is preferred that a (imino group is towards the X or Y).
- R 5 and R 6 independently represent a hydrogen atom, a halogen atom, and an alkyl group (preferably having 1 to 6 carbon atoms).
- R 7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- La is a structural site that forms a ring structure with CR 8 CR 9 and N atoms.
- La is preferably a structural site that forms a non-aromatic heterocycle having 3 to 7 carbon atoms in combination with the carbon atom of CR 8 CR 9. More preferably, La is a structural site in which the carbon atom and N atom (nitrogen atom) of CR 8 CR 9 are combined to form a 5- to 7-membered non-aromatic heterocycle. More preferably, La is a structural site that forms a 5-membered non-aromatic heterocycle, and is particularly preferably a structural site that forms pyrrolidine. La may further have a substituent such as an alkyl group.
- X represents a group having a functional group of pKa14 or less.
- Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.
- the dispersant (oligoimine-based dispersant) is further copolymerized with one or more selected from the repeating units represented by the formulas (I-3), (I-4), and (I-5). It may be contained as an ingredient.
- the dispersant contains such a repeating unit, the dispersion performance of the filler can be further improved.
- R 1 , R 2 , R 8 , R 9 , L, La, a and * are synonymous with the provisions in formulas (I-1), (I-2) and (I-2a).
- Ya represents an oligomer chain or polymer chain having an anionic group and having 40 to 10,000 atoms.
- the oligoimine-based dispersant is, for example, the following resin X-4 or the resin described in paragraphs 0169 to 0190 of Japanese Patent Application Laid-Open No. 2015-034961.
- the dispersant is also available as a commercial product.
- Such dispersants are, for example, "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110, 180 (copolymer containing an acid group), 130 (polypolymer) manufactured by BYK Chemie Co., Ltd. , 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ", BYK Chemie Co., Ltd.”
- BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ", EFKA Co., Ltd.
- EFKA4047, 4050, 4010, 4165 polyurethane type
- EFKA4330, 4340 block copolymer
- 4400 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (Fatile polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Azisper PB821, PB822 ”manufactured by Ajinomoto Fine Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd., Kyoeisha Chemical Co., Ltd. "Polyflow No. 50E, No.
- Nonylphenyl ether ”, Acetamine 86 (stearylamine acetate)”, Lubrizol Co., Ltd. “Solsperse 5000” (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 26000, 28000, 32000, 36000, 38500 (graft type polymer), 41000 ", Nikko Chemicals Co., Ltd.”
- Nikkor T106 polyoxyethylene sorbitan monooleate
- MYS-IEX polyoxyethylene monostearate
- a dispersant having a phosphorus atom-containing group for example, a phosphoric acid group
- a phosphorus atom-containing group for example, a phosphoric acid group
- “Solsperse 26000, 36000, 41000” manufactured by Lubrizol Co., Ltd. can be mentioned. ..
- the content of the dispersant is preferably 0.1 to 50% by mass with respect to 100 parts by mass of the filler.
- the upper limit is preferably 40 parts by mass or less, and more preferably 30% by mass or less.
- the lower limit is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more.
- the resin used for the heat conductive layer of the present invention can contain polyimide, polybenzoxazole and precursors thereof.
- the polyimide precursor and the polybenzoxazole precursor contained in the composition of the present invention become a polyimide resin and a polybenzoxazole resin by forming a coating film of the composition and then cyclizing it.
- Polyimide precursors and polybenzoxazole precursors are preferably used for negative development.
- the resin of the present invention preferably contains a polyimide precursor.
- polyimide resin and the polyimide precursor are described in paragraphs 0014 to 0046 of International Publication No. 2018/043467, and the contents thereof are incorporated in the present specification.
- the composition used for producing the heat conductive layer of the present invention preferably contains a polymerizable compound.
- a polymerizable compound a compound having at least one ethylenically unsaturated double bond is preferable, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more is more preferable.
- the polymerizable compound is preferably a compound having 6 or more ethylenically unsaturated double bonds or a compound having 3 to 4 ethylenically unsaturated double bonds, and is preferably an ethylenically unsaturated double bond. A compound having 3 to 4 bonds is more preferable.
- the group having an ethylenically unsaturated bond is preferably a (meth) acryloyl group or a (meth) acryloyloxy group.
- the polymerizable compound is preferably a radically polymerizable compound.
- the polymerizable compound preferably contains a compound having at least two or more in the molecule selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group.
- the number of carbon atoms in the alkyl chain in the alkoxymethyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 or 2. That is, the alkoxymethyl group is preferably a methoxymethyl group or an ethoxymethyl group.
- the molecular weight of the polymerizable compound of the present invention is preferably 100 to 3000.
- the upper limit is preferably less than 2000, more preferably less than 1000.
- the lower limit is preferably 150 or more, and more preferably 250 or more.
- the polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functions, more preferably a (meth) acrylate compound having 3 to 6 functions, and a (meth) acrylate compound having 3 to 4 functions. Is even more preferable. According to this aspect, the solvent resistance of the obtained film and the adhesion to the base material can be improved.
- the polymerizable compound is also preferably a hexafunctional or higher functional (meth) acrylate compound.
- the polymerizable compound is preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated bond having a boiling point of 100 ° C. or higher under normal pressure.
- monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylol ethanetri (meth).
- the polymerizable compounds are pentaerythritol tetraacrylate (commercially available: A-TMMT; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and dipentaerythritol triacrylate (commercially available: KAYARAD D-330; Nippon Kayaku Co., Ltd.).
- Dipentaerythritol tetraacrylate (commercially available, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available, KAYARAD D-310; Japan) Yakuhin Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) are preferable, and pentaerythritol tetraacrylate is more preferable.
- the polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group.
- a polymerizable compound having an acid group can be obtained by a method such as (meth) acrylate-forming some hydroxyl groups of a polyfunctional alcohol and adding an acid anhydride to the remaining hydroxyl groups to form a carboxyl group.
- Examples of the polymerizable compound having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid.
- the polymerizable compound having an acid group is preferably a compound having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
- the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
- examples of commercially available products include M-305, M-510, and M-520 of the Aronix series as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g.
- the lower limit is preferably 5 mgKOH / g or more.
- the upper limit is preferably 30 mgKOH / g or less.
- the polymerizable compound is a polymerizable compound having a caprolactone structure.
- the polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include ⁇ -caprolactone-modified polyfunctional (meth) acrylate.
- ⁇ -caprolactone-modified polyfunctional (meth) acrylates include, for example, trimethylolethane, dimethylolethane, trimethylolpropane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and the like. It is obtained by esterifying (meth) acrylic acid and ⁇ -caprolactone with the polyhydric alcohol of.
- the polymerizable compound includes urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-0371993, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
- addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are also preferable.
- urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), U-4HA, U-6LPA, UA-32P, U-10HA, U-10PA, etc.
- UA-122P, UA-1100H, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600 , T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), UA-9050, UA-9048 (manufactured by BASF Co., Ltd.) and the like.
- the details of the structure, single use or combined use, addition amount, and other usage methods can be arbitrarily set according to the final performance design of the composition.
- a structure having a high unsaturated group content per molecule is preferable, and in many cases, bifunctionality or higher is preferable.
- a trifunctional or higher functional compound is preferable, and a plurality of compounds having different functional numbers and types of polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether) are preferable.
- a method of adjusting both sensitivity and intensity by using a system compound) in combination is also effective.
- a polymerizable compound which is a trifunctional or higher functional compound and has a different ethylene oxide chain length in combination.
- the developability of the composition can be adjusted, and an excellent pattern shape can be obtained.
- the selection and usage of the polymerizable compound is also an important factor for the compatibility and dispersibility with other components (for example, photopolymerization initiator, resin, etc.) contained in the composition, and for example, Compatibility and the like can be improved by using a low-purity compound or using two or more kinds in combination.
- the content of the polymerizable compound is preferably 0.5 to 50% by mass with respect to the total solid content in the composition.
- the lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more.
- the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
- the composition used for producing the heat conductive layer of the present invention preferably contains a compound having an epoxy group (hereinafter, also referred to as "epoxy compound").
- the epoxy compound can improve the solvent resistance of the obtained film.
- the epoxy compound may be, for example, a cross-linking agent described later.
- examples of the epoxy compound include monofunctional or polyfunctional glycidyl ether compounds and polyfunctional aliphatic glycidyl ether compounds.
- a compound having an epoxy group such as glycidyl (meth) acrylate or allyl glycidyl ether as a part of the glycidyl group, or an alicyclic epoxy compound can also be used.
- Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule. It is preferable to have 1 to 100 epoxy groups in one molecule.
- the upper limit may be, for example, 10 or less, or 5 or less.
- the lower limit is preferably two or more.
- the epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 2000, further, a molecular weight of less than 1000), or a polymer compound (for example, a molecular weight of 1000 or more, further a molecular weight of 2000 or more, and in the case of a polymer, the weight.
- the average molecular weight may be 1000 or more, and the weight average molecular weight may be 2000 or more).
- the weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000.
- the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
- bisphenol F type epoxy resin for example, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21. , RE-602S (manufactured by Nippon Kayaku Co., Ltd.) and the like can be used.
- phenol novolac type epoxy resin for example, jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation). ), Etc. can be used.
- cresol novolac type epoxy resin for example, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, DIC).
- EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.
- an aliphatic epoxy resin for example, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (all manufactured by ADEKA Corporation), celoxide 2021P, celoxide 2081, celoxide 2083, celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), etc.
- ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (all manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation) and the like can be used.
- the epoxy compound a compound having an epoxy group as a part of the glycidyl group, for example, glycidyl (meth) acrylate or allyl glycidyl ether can also be used.
- unsaturated compounds having an alicyclic epoxy group are preferable.
- the description in paragraph 0045 of JP-A-2009-265518 can be referred to, and these contents are incorporated in the present specification.
- the content of the epoxy compound is preferably 0.01 to 50% by mass with respect to the total solid content in the composition.
- the lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more.
- the upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less.
- the epoxy compound may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount thereof is in the above range.
- a particularly preferable cross-linking agent is a phenol derivative having 3 to 5 benzene rings in the molecule, having at least 2 or more selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, and having a molecular weight of 1200 or less.
- examples thereof include a melamine-formaldehyde derivative having at least two free N-alkoxymethyl groups and an alkoxymethylglycol uryl derivative.
- the composition used for producing the heat-conducting layer of the present invention preferably contains at least two compounds having two or more alkoxymethyl groups in the molecule as a cross-linking agent, and is more preferably alkoxymethyl. It is more preferable to contain at least two types of phenolic compounds having two or more groups in the molecule, and at least one of the above at least two types of phenolic compounds contains 3 to 5 benzene rings in the molecule, and further. It is particularly preferable that the phenol derivative has two or more alkoxymethyl groups in total and has a molecular weight of 1200 or less. As the alkoxymethyl group, a methoxymethyl group and an ethoxymethyl group are preferable.
- a phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound having no corresponding hydroxymethyl group with formaldehyde under a base catalyst. Further, the phenol derivative having an alkoxymethyl group can be obtained by reacting the phenol derivative having the corresponding hydroxymethyl group with an alcohol under an acid catalyst.
- a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of sensitivity and storage stability.
- Examples of another preferred cross-linking agent include compounds having an N-hydroxymethyl group or an N-alkoxymethyl group, such as an alkoxymethylated melamine-based compound, an alkoxymethyl glycol ureyl-based compound, and an alkoxymethylated urea-based compound. Can be done.
- Examples of such a compound include hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylglycoluryl, 1,3-bismethoxymethyl-4,5-bismethoxyethyleneurea, bismethoxymethylurea and the like, and European patents. It is disclosed in Patent Application Publication No. 0133216, European Patent Application Publication No. 021482, German Patent Application Publication No. 3634671, and German Patent Application Publication No. 371164.
- cross-linking agents the ones that are particularly preferable are listed below.
- cross-linking agent is preferably the following compound.
- the cross-linking agent is preferably added in an amount of 3 to 65% by mass, more preferably 5 to 50% by mass, based on the total solid content in the composition for forming a heat conductive layer of the present invention.
- the addition amount of the cross-linking agent By setting the addition amount of the cross-linking agent to 3 to 65% by mass, it is possible to prevent the residual film ratio and the resolving power from being lowered, and to maintain good stability of the composition during storage.
- the amount of the cross-linking agent added means the amount including the epoxy compound.
- the composition used for producing the heat conductive layer of the present invention preferably contains a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators.
- a compound having photosensitivity to light rays in the ultraviolet region to the visible region, active light rays, or radiation is preferable.
- the photopolymerization initiator is preferably a photoradical polymerization initiator or a compound that generates an acid by irradiation with active light or radiation.
- the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
- the photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like can be mentioned.
- the halogenated hydrocarbon compound having a triazine skeleton examples include Wakabayashi et al., Bull. Chem. Soc.
- trihalomethyltriazine compound trihalomethyltriazine compound, benzyldimethylketal compound, ⁇ -hydroxyketone compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium compound.
- aminoacetophenone-based initiator commercially available products IRGACURE 907 and IRGACURE 369, and IRGACURE 379 and IRGACURE 379EG (trade names: all manufactured by BASF Corporation) can be used.
- aminoacetophenone-based initiator the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
- acylphosphine-based initiator commercially available products IRGACURE 819 and IRGACURE TPO (trade names: both manufactured by BASF Corporation) can be used. Acylphosphine-based initiators are preferable from the viewpoint of preventing coloration after exposure.
- An oxime compound can also be preferably used as the photopolymerization initiator.
- the oxime compound the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
- Examples of the oxime compound that can be preferably used in the present invention include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminovtan-2-one, and 2 -Acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2 -On, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one and the like can be mentioned.
- J. C. S. Perkin II (1979) pp.
- paragraphs 0274 to 0275 of JP2013-209760A can be referred to, and the contents thereof are incorporated in the present specification.
- an oxime compound having a fluorene ring can also be used as the photopolymerization initiator.
- Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466. This content is incorporated herein.
- an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like. This content is incorporated herein.
- an oxime compound having a nitro group can be used as the photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466, and Patent No. Examples thereof include the compounds described in paragraphs 0007 to 0025 of Japanese Patent Application Laid-Open No. 4223071, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
- the oxime compound is preferably a compound having an absorption maximum wavelength in the wavelength region of 350 nm to 500 nm, more preferably a compound having an absorption maximum wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably a compound having a high absorbance at 365 nm and 405 nm.
- the molar extinction coefficient at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 5,000 to 300,000 from the viewpoint of sensitivity. It is particularly preferably 200,000.
- the molar extinction coefficient of the compound can be measured using a known method. Specifically, for example, an ethyl acetate solvent is used with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.). It is preferable to measure at a concentration of 0.01 g / L.
- composition used for producing the heat conductive layer of the present invention contains a compound that generates an acid by irradiation with active light or radiation (hereinafter, also simply referred to as "acid generator") as a photopolymerization initiator. You may.
- the acid generator may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Further, the form of the low molecular weight compound and the form incorporated in a part of the polymer may be used in combination.
- the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
- the acid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the above-mentioned acid-degradable resin, or may be incorporated in a resin different from the acid-degradable resin.
- An onium salt compound can be mentioned as a preferable form of the acid generator.
- Examples of such onium salt compounds include sulfonium salts, iodonium salts, phosphonium salts and the like.
- the acid generator a compound that generates sulfonic acid, imic acid or methidoic acid by irradiation with active light or radiation can be mentioned.
- the acid generator in that form include a sulfonium salt, an iodonium salt, a phosphonium salt, an oxime sulfonate, and an imide sulfonate.
- the acid generator is preferably a compound that generates an acid by irradiation with an electron beam or extreme ultraviolet rays.
- the compound is an acid having a volume of 130 ⁇ 3 or more (more preferably) from the viewpoint of suppressing the diffusion of the exposed acid into the non-exposed portion and improving the resolution and the pattern shape.
- It is preferably a compound that generates sulfonic acid), more preferably a compound that generates an acid having a volume of 190 ⁇ 3 or more (more preferably sulfonic acid), and an acid having a volume of 270 ⁇ 3 or more (more preferably). More preferably, it is a compound that generates sulfonic acid), and it is particularly preferable that it is a compound that generates an acid (more preferably sulfonic acid) having a volume of 400 ⁇ 3 or more.
- the volume is preferably at 2000 ⁇ 3 or less, and more preferably 1500 ⁇ 3 or less.
- the above volume value was obtained using the molecular orbital calculation software "WinMOPAC" manufactured by Fujitsu Limited.
- the acid generator preferably onium compound used in the present invention
- a high molecular compound in which a group that generates an acid (photoacid generating group) by irradiation with active light or radiation is introduced into the main chain or side chain of the polymer compound.
- Molecular acid generators can also be used.
- the content of the acid generator in the composition is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, still more preferably, based on the total solid content in the composition. Is 1 to 18% by mass.
- the acid generator can be used alone or in combination of two or more. When two or more acid generators are used in combination, the total amount thereof is preferably included in the above range.
- a photopolymerization initiator having an extinction coefficient of 365 nm in methanol of 1.0 ⁇ 10 3 mL / gcm or more and an extinction coefficient of 365 nm in methanol of 1.0 ⁇ 10 2 mL / gcm or less it is also preferable to use in combination with a photopolymerization initiator having an extinction coefficient of 254 nm of 1.0 ⁇ 10 3 mL / g cm or more.
- Specific examples include the combined use of an aminoacetophenone compound and an oxime compound.
- a film having excellent curability can be produced even under low temperature conditions.
- the composition in the pattern forming step, by exposing the composition in two steps, before the developing step and after the developing step, the composition can be appropriately cured in the first exposure, and the entire composition can be substantially cured in the next exposure. Can be cured. Therefore, the curability of the composition can be improved even under low temperature conditions.
- the content of the photopolymerization initiator is preferably 0.01 to 50% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5, based on the total solid content in the composition. ⁇ 10% by mass. In this range, better sensitivity and pattern formation can be obtained.
- the composition may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
- the composition used for producing the heat conductive layer of the present invention preferably contains a solvent.
- a solvent a known solvent can be arbitrarily used.
- the solvent is preferably an organic solvent.
- the organic solvent include compounds such as alcohols, esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
- ketones for example, acetone, acetylacetone, methyl ethyl ketone, diacetone alcohol, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
- organic solvents for example, ethylene dichloride and the like are preferable.
- the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ⁇ -butyrolactone.
- Dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and a mixed solution composed of two or more selected from propylene glycol methyl ether acetate are preferable.
- the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
- the content of the solvent is appropriately adjusted according to the content and conditions of the application method within the range in which the composition for forming a heat conductive layer can be applied on the support.
- the content of the solvent is preferably an amount such that the solid content concentration in the heat conductive layer forming composition is 5 to 80% by mass. That is, the content of the solvent is preferably 20 to 95% by mass in the composition.
- a composition for forming a heat conductive layer having a relatively high viscosity for example, 10 to 1000 mPa ⁇ s, preferably 20 to 200 mPa ⁇ s
- a spin coating method for example, when a spin coating method is used
- the upper limit of the solid content concentration in the composition is more preferably 75% by mass or less, further preferably 70% by mass or less, and particularly preferably 65% by mass or less.
- the lower limit of the solid content concentration in the heat conductive layer forming composition is more preferably 35% by mass or more, further preferably 45% by mass or more, and further preferably 50% by mass or more. Is particularly preferable.
- a solvent having a low metal content it is preferable to use a solvent having a low metal content.
- the metal content of the solvent is preferably, for example, 10 ppb or less. If necessary, a ppt level solvent may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
- Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
- the filter pore diameter of the filter used for filtration is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less.
- a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
- the solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
- the composition used in the production of the heat conductive layer of the present invention can contain an adhesive, and the adhesive is, for example, a silane coupling agent.
- the adhesion between the base material such as a wafer or the base material such as metal wiring and the film can be improved.
- the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
- the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction.
- the content of the adhesive is preferably 0.001 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, based on the total solid content in the composition.
- the adhesive may be only one type or two or more types. In the case of two or more kinds, it is preferable that the total amount thereof is in the above range.
- the composition used in the production of the heat conductive layer of the present invention preferably further contains a cosensitizer.
- the co-sensitizer has actions such as further improving the sensitivity of the photopolymerization initiator and the sensitizer to active radiation, and suppressing the polymerization inhibition of the polymerizable compound by oxygen.
- the cosensitizer for example, the description of paragraphs 0254 to 0257 of JP2010-106268A (corresponding US Patent Application Publication No. 2011/0124824, ⁇ 0277> to ⁇ 0279>) can be referred to. Is incorporated herein by reference.
- the composition used in the production of the heat conductive layer of the present invention is capable of unnecessarily polymerizing a compound having an ethylenically unsaturated double bond (for example, a polymerizable compound) that can be polymerized during the production or storage of the composition. It preferably contains a polymerization inhibitor to prevent it.
- Polymerization inhibitors are, for example, the following compounds; Phenolic hydroxyl group-containing compounds (preferably hydroquinone, 4-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol) ), 2,2'-Methylenebis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol (BHT), phenolic resins, and cresol resins.
- Phenolic hydroxyl group-containing compounds preferably hydroquinone, 4-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol)
- 2,2'-Methylenebis (4-methyl-6-t-butylphenol) 2,6-di-t-butyl
- N-oxide compounds preferably 5,5-dimethyl-1-pyrrolin N-oxide, 4-methylmorpholin N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide , A compound selected from the group consisting of picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide
- Piperidine 1-oxyl free radical compounds preferably piperidine 1-oxyl free radical, 2,2,6,6-tetramethyl piperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethyl Piperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 4-acetamide-2,2,6,6-tetramethylpiperidin 1-oxyl free radical, A compound selected from the group consisting of 4-maleimide-2,2,6,6-tetramethylpiperidin 1-oxyl free radical and 4-phosphonooxy-2,2,6,6
- Pyrrolidine 1-oxyl free radical compounds preferably 3-carboxyproxyl free radicals (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radicals)
- N-nitrosophenylhydroxylamines preferably compounds selected from the compound group consisting of N-nitrosophenylhydroxylamine first cerium salt and N-nitrosophenylhydroxylamine aluminum salt
- Diazonium compounds selected from the group consisting of hydrogen sulfate of 4-diazophenyldimethylamine, tetrafluoroborate of 4-diazodiphenylamine, and hexafluorophosphate of 3-methoxy-4-diazodiphenylamine.
- Compound Compound); Cationic dyes; Sulfide group-containing compounds; Nitro group-containing compounds; Transition metal compounds such as FeCl 3 and CuCl 2.
- polymerization inhibitor examples include the compounds described in paragraphs 0211 to 0223 of JP2015-034961A, the contents of which are incorporated in the present specification.
- the content of the polymerization inhibitor is preferably 0.01% by mass to 10% by mass, more preferably 0.01 to 8% by mass, and 0.01 to 5% with respect to the photopolymerization initiator. Most preferably, it is by mass. Within the above range, the curing reaction is sufficiently suppressed in the non-exposed area and the curing reaction is sufficiently promoted in the exposed area, and the image formability and sensitivity are improved.
- the polymerization inhibitor may be only one kind or two or more kinds. In the case of two or more kinds, it is preferable that the total amount thereof is in the above range.
- the composition used for producing the heat conductive layer of the present invention may contain various surfactants from the viewpoint of further improving the coatability.
- various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
- the liquid characteristics when prepared as a coating liquid are further improved. Therefore, the uniformity of the coating thickness and the liquid saving property can be further improved.
- the wettability to the surface to be coated is reduced by reducing the interfacial tension between the surface to be coated and the coating liquid. Is improved, and the applicability to the surface to be coated is improved. Therefore, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.
- the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass.
- the lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more.
- the upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less.
- fluorine-based surfactant for example, the surfactant described in paragraphs 0060 to 0064 of JP2014-014318 (corresponding paragraphs 0060 to 0064 of International Publication No. 2014/017669), JP-A-2011-132503.
- the surfactants described in paragraphs 0117 to 0132 of the publication can be used. These contents are incorporated in the present specification.
- Examples of commercially available fluorine-based surfactants include Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, and the same.
- the composition used for producing the heat conductive layer of the present invention may contain an ultraviolet absorber.
- an ultraviolet absorber a conjugated diene compound is preferable, and a compound represented by the following formula (I) is more preferable.
- R 1 and R 2 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 are They may be the same or different from each other, but they do not represent hydrogen atoms at the same time.
- R 1 and R 2 may form a cyclic amino group with the nitrogen atom to which R 1 and R 2 are attached.
- the cyclic amino group is, for example, a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazepino group, a piperazino group and the like.
- R 3 and R 4 each independently represent an electron attracting group.
- the electron attracting group is an electron attracting group having a Hammett substituent constant ⁇ p value (hereinafter, simply referred to as “ ⁇ p value”) of 0.20 or more and 1.0 or less.
- ⁇ p value Hammett substituent constant
- R 3 and R 4 may combine with each other to form a ring.
- At least one of the above R 1 , R 2 , R 3 , and R 4 may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.
- the ultraviolet absorber represented by the formula (I) is, for example, a compound having the following structure.
- paragraphs 0024 to 0033 of International Publication No. 2009/123109 (corresponding US Patent Application Publication No. 2011/0039195, ⁇ 0040> to ⁇ 0059>. >) Can be taken into account and these contents are incorporated herein by reference.
- Preferred specific examples of the compound represented by the formula (I) are, for example, an example of paragraphs 0034 to 0037 of International Publication No. 2009/123109 ( ⁇ 0060> of the corresponding US Patent Application Publication No. 2011/0039195).
- the composition of the present invention preferably further contains a migration inhibitor.
- a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the film.
- Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
- the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520 can be used.
- the composition of the present invention may contain a curing accelerator.
- the curing accelerator may be a thermosetting accelerator or a photocuring accelerator.
- the curing accelerator is preferably a thermosetting accelerator.
- the thermosetting accelerator preferably generates a base by heating.
- Such a thermosetting accelerator is preferably, for example, the following compound.
- thermosetting accelerator examples include acidic compounds that generate bases when heated to 40 ° C. or higher and ammonium salts having pKa1 of 0 to 4 anions and ammonium cations described in International Publication No. 2015/199219. These contents are incorporated in the present specification.
- the content of the thermosetting accelerator in the composition is preferably 0.01 to 50% by mass with respect to the total solid content in the composition.
- the lower limit is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more.
- the upper limit is more preferably 10% by mass or less, further preferably 5% by mass or less.
- the composition may contain known additives such as a plasticizer and a fat-sensing agent in order to improve the physical characteristics of the cured film.
- Plasticizers include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like.
- the content of the plasticizer is preferably 10% by mass or less with respect to the total mass of the polymerizable compound and the resin.
- O-180A manufactured by ADEKA
- a process of dispersing the filler a process of using compression, squeezing, impact, shearing, cavitation, etc. as a mechanical force used for dispersing the filler can be mentioned. Specific examples of these processes include bead mills, sand mills, roll mills, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, ultrasonic dispersion, and the like.
- the composition can be agitated using, for example, a stirrer (stirrer) or a stirring blade.
- the rotation speed is preferably, for example, 10 to 2000 rpm.
- the lower limit is preferably 100 rpm or more, more preferably 300 rpm or more.
- the upper limit is preferably 1500 rpm or less, more preferably 1000 rpm or less.
- the stirring can be performed by a method such as bubbling or ultrasonic waves.
- a conventionally known storage container can be used as the storage container for the composition of the present invention.
- the inner wall of the container is made of a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are formed into a 7-layer structure. It is also preferable to use a bottle of resin. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
- filtering by the first filter may be performed only once or twice or more.
- filtering with the first filter may be performed only with the dispersion liquid, and after mixing other components, filtering with the second filter may be performed.
- first filters having different pore diameters within the above-mentioned range may be combined.
- the nominal value of the filter manufacturer can be referred to.
- select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can do.
- the second filter one formed of the same material as the first filter described above can be used.
- the laminate 5 of the present invention has a base material 1 and a heat conductive layer 4 or a dry film of the present invention formed on the base material 1.
- This laminated body may further have an endothermic portion in contact with the heat conductive layer.
- the endothermic unit is a cooling module, for example, a heat radiation fin, a heat pipe, a Peltier module, a cooling plate, and the like.
- the semiconductor device of the present invention is a semiconductor device having the heat conductive layer or laminate of the present invention.
- the heat conductive layer of the present invention is suitably used as an insulating layer or an adhesive layer in the semiconductor module 8 as shown in FIG. 6, for example.
- the semiconductor module 8 of FIG. 6 has a support substrate 10, a lid 11 bonded to the support substrate 10 by the adhesive layer 20, and a cooling module 15 bonded to the lid 11 by the adhesive layer 23.
- the semiconductor module 8 has a laminated chip in which a first semiconductor chip 12 and a second semiconductor chip 13 are bonded via an intermediate layer 25 in a space formed between a support substrate 10 and a lid 11.
- FIG. 7 is a partially enlarged view of the region A in FIG.
- the first semiconductor chip 12 has an LSI chip 32 and a wiring layer 32a formed on the surface of the LSI chip 32 on the intermediate layer 25 side.
- the second semiconductor chip 13 has an LSI chip 33 and a wiring layer 33a formed on the surface of the LSI chip 33 on the intermediate layer 25 side.
- the intermediate layer 25 has a solder bump 35a that electrically connects the wiring layers 32a and 33a, and has a resin insulating layer 35b that fills the periphery of the solder bump 35a.
- the first semiconductor chip 12 and the second semiconductor chip 13 are electrically connected to each other via the solder bumps 35a, and integrally form a laminated LSI.
- FIG. 8 is a conceptual diagram showing a part of the manufacturing process of the laminated LSI as described above.
- the photosensitive composition of the present invention is applied to the surface of a semiconductor wafer (wafer on which a semiconductor device, a first semiconductor chip 12, or the like is formed) and dried to form a dry film 35c (FIG. 8a).
- a hole 36 or a desired pattern having a desired cross section is formed on the dry film 35c, and the wiring layer 32a of the semiconductor chip 12 is formed.
- a part of (electrode) is exposed (Fig. 8b).
- an intermediate layer 25 having the solder bumps 35a and the resin insulating layer 35b that fills the periphery thereof can be obtained (FIG. 8c).
- the wiring layer 33a (electrode) of the second semiconductor chip 13 in a state of being temporarily adhered to the intermediate layer 25, the wiring layer 33a and the solder bump 35a can be electrically connected ().
- FIG. 8d the intermediate layer 25 contains the resin insulating layer 35b, which is the heat conductive layer of the present invention, so that heat is efficiently transferred to the solder bumps while maintaining excellent insulating properties, and solder connection is performed. it can.
- a conductive paste may be used instead of the solder bumps.
- the conductive paste is, for example, a bonding material in which a resin responsible for fixing and a metal (conductive filler) responsible for conductivity are mixed, and has both a property of conducting electricity and a property of fixing substances to each other.
- epoxy resin and silver (Ag) filler are often combined.
- the joint surfaces are joined to each other using the conductive paste, and then heat is applied to cure the conductive paste, so that the joint surfaces are joined after ensuring conductivity.
- the heating conditions at the time of joining are, for example, about 150 ° C. for about 30 minutes.
- the conductive paste for example, the following commercially available products can be used. Made by Nihon Handa Co., Ltd. Product name: Dodent Model number NH-070A (L) Made by ThreeBond Co., Ltd. Product name: 3300 series Model number 380B Two-component epoxy conductive adhesive
- a method for forming a patterned heat-conducting layer of the present invention in addition to the photolithography method as described above, conventionally known methods such as a screen printing method and an inkjet printing method are known. A printing method can be used. Furthermore, a method of mechanically removing a part of the continuous film-like heat conductive layer can also be used. For example, on a semiconductor wafer with copper pillars, a continuous film-like heat-conducting layer having a thickness sufficient to fill the gaps between the copper pillars is formed, and then a part of the heat-conducting layer is formed by using an instrument such as a grinder. The heat transfer layer can be patterned by mechanically removing the copper pillars to expose the copper pillars.
- the semiconductor chip can be manufactured by dicing the semiconductor wafer. Then, in the method for manufacturing a semiconductor device as described above, a joining method using a solder bump or a conductive paste is appropriately selected according to the type of the object to be joined. For example, when the objects to be bonded are a semiconductor wafer and a semiconductor chip, they can be bonded using a chip-on-wafer bonding device. Further, when the objects to be bonded are semiconductor wafers, they can be bonded using a device for wafer-wafer bonding, and when the objects to be bonded are semiconductor chips, chip-chip bonding can be performed. These can be joined using the device for.
- As equipment for chip-chip bonding and chip-on-wafer bonding for example, bonding equipment of Toray Engineering Co., Ltd., Shibuya Industry Co., Ltd., Shinkawa Co., Ltd., Hyundai Motor Co., Ltd., etc. Can be used.
- As a device for wafer-wafer bonding for example, Mitsubishi Heavy Industries Machine Tool Co., Ltd., Bond Tech Co., Ltd., PMT Co., Ltd., Ayumi Kogyo Co., Ltd., Tokyo Electron Limited (TEL), EVG, etc.
- Joining devices of various companies such as SUSS MicroTec Co., Ltd. and Musashino Engineering Co., Ltd. can be used. After the above joining, by putting it in a reflow furnace, the reliability of electrical joining by solder bumps or conductive paste can be improved.
- the heat conductive layer of the present invention can also be used as a pre-coated wafer level NCP (Non-Conductive Paste) and a pre-coated panel level NCP (Non-Conductive Paste).
- an electronic circuit including the heat conductive layer of the present invention as a non-conductive portion is collectively formed on a circular substrate such as a semiconductor wafer or a square substrate such as a panel, and then this substrate is fragmented (processed into a chip). By doing so, it is also possible to manufacture a semiconductor chip.
- the productivity of the semiconductor device is further improved.
- the heat conductive layer of the present invention can also be used for die attach (fixation of a semiconductor chip to an adherend).
- the atmosphere at the time of joining can be selected from an inert atmosphere such as a nitrogen atmosphere, a decompression atmosphere including a vacuum atmosphere, and a reducing atmosphere such as hydrogen and formic acid, including the atmosphere.
- an inert atmosphere oxidation of the electrode surface of the semiconductor device can be suppressed.
- a reduced pressure atmosphere the generation of voids can be suppressed.
- good bonding can be achieved even if the electrode surface of the semiconductor device is oxidized.
- the heating temperature at the time of joining is not particularly limited to the above, and can be selected within the range of 100 to 400 ° C.
- the pressure (load) at the time of joining is also not particularly limited, and it is possible to pressurize rapidly or stepwise according to physical characteristics such as the strength of the object to be joined.
- the exposed electrode obtained by patterning the heat conductive layer of the present invention by the above method can be used for bonding with a bonding wire in addition to the flip chip bonding shown above.
- the heat conductive layer of the present invention is, for example, bonded between the adhesive layers 20 to 23 and the resin insulating layer 35b, particularly between the semiconductor chip which is a heat source and the cooling module. It is used for the portions of the layers 22 and 23 and the resin insulating layer 35b.
- the present invention can be applied to logic integrated circuits such as ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), and ASSP (Application Specific Standard Product), for example. Further, the present invention can be applied to, for example, a microprocessor such as a CPU (Central Processing Unit) and a GPU (Graphics Processing Unit). Further, the present invention provides, for example, DRAM (Dynamic Random Access Memory), HMC (Hybrid Memory Cube), MRAM (Magnetoresistive Random Access Memory), PCM (Phase-Change Memory), ReRAM (Resistance Random Access Memory), FeRAM (Ferroelectric). It can also be applied to memories such as RandomAccessMemory) and flash memory.
- ASIC Application Specific Integrated Circuit
- FPGA Field Programmable Gate Array
- ASSP Application Specific Standard Product
- the present invention can be applied to, for example, a microprocessor such as a CPU (Central Processing Unit) and a GPU (Graphics Processing Unit).
- the present invention also applies to analog integrated circuits such as LEDs (Light Emitting Diodes), power devices, DC (Direct Current) -DC (Direct Current) converters, and insulated gate bipolar transistors (IGBTs). Applicable.
- the present invention is also applicable to MEMS (Micro Electro Mechanical Systems) such as acceleration sensors, pressure sensors, oscillators, and gyro sensors. Further, the present invention relates to, for example, GPS (Global Positioning System), FM (Frequency Modulation), NFC (Near field communication), RFEM (RF Expansion Module), MMIC (Monolithic Microwave Integrated Circuit), WLAN (Wireless Local Area Network).
- GPS Global Positioning System
- FM Frequency Modulation
- NFC Near field communication
- RFEM RF Expansion Module
- MMIC Monitoring Microlithic Microwave Integrated Circuit
- WLAN Wireless Local Area Network
- CMOS Complementary Metal Oxide Semiconductor
- CMOS image sensors Camera modules
- Passive devices SAW (Surface Acoustic Wave) filters
- RF (Radio Frequency) filters IPD (Integrated Passive Devices), etc. Applicable.
- the heat conductive layer of the present invention is not limited to the adhesion of semiconductor devices as described above, and can be applied to, for example, adhesion between a housing of an electronic device and parts such as a battery, a substrate, and a cooling module (heat pipe, etc.). is there. Further, the heat conductive layer of the present invention can also be applied to adhesion of parts such as in-vehicle electronic devices, batteries, and power conversion devices to a cooling device using an air cooling mechanism or a water cooling mechanism.
- the heat conductive layer of the present invention can be used for applications other than adhesion.
- the heat conductive layer of the present invention can be used as a fine heat radiation fin.
- Dispersion treatment conditions ⁇ Bead material: Zirconia ⁇ Bead diameter: 0.2 mm in diameter -Bead filling rate: 65% by volume ⁇ Peripheral speed: 6 m / sec ⁇ Pump supply amount: 10.8 kg / hour ⁇ Cooling water: Tap water ⁇ Bead mill annular passage internal volume: 0.15 L -Amount of mixed liquid to be dispersed: 0.65 kg
- L-1 Alumina (average primary particle size 3 ⁇ m, aspect ratio 1). Sumiko Random AA-3 manufactured by Sumitomo Chemical Co., Ltd.
- L-2 Alumina (average primary particle size 0.7 ⁇ m, aspect ratio 1). Sumitomo Chemical Co., Ltd., Sumiko Random AA-07.
- M-1 Alumina (average primary particle size 0.4 ⁇ m, aspect ratio 1). Sumitomo Chemical Co., Ltd., Sumiko Random AA-04. -M-2: Alumina (average primary particle size 0.3 ⁇ m, aspect ratio 1). Sumitomo Chemical Co., Ltd., Sumiko Random AA-03F.
- composition for forming a heat conductive layer Each material was blended and mixed so as to have the blending ratio (parts by mass) shown in Table 2 below. Then, the heat conductive layer forming compositions Y-1 to Y-9 are adjusted by filtering the above mixture using a polytetrafluoroethylene (PTFE) membrane filter (manufactured by Wintech) having a pore size of 20 to 30 ⁇ m. did.
- PTFE polytetrafluoroethylene
- X-1 to X-5 are the dispersions X-1 to X-5 prepared above, respectively.
- a heat conductive layer was prepared by the following procedure by a spin coating method, a spray coating method or a slit coating method.
- -Time t 3 The time when the solid content concentration of the heat conductive layer forming composition reached the second threshold concentration.
- the silicon wafer was installed on the rotation stage so that the position of the center of gravity of the silicon wafer overlapped with the rotation center of the rotation stage in the horizontal direction, and the rotation stage was set to rotate clockwise (clockwise).
- the heat conductive layer forming composition was discharged from the nozzle of the spin coater toward the position of the center of gravity of the silicon wafer, and the heat conductive layer forming composition was supplied onto the silicon wafer.
- the distance between the nozzle and the support was 25 mm.
- the rotation speed of the rotating stage is quickly increased to 1000 rpm (meaning a change within a time of less than 1 second, and the same applies hereinafter), and the state of 1000 rpm is maintained. did.
- the first solvent weight loss time T 1 was 10 seconds.
- the amount of the heat conductive layer forming composition supplied was adjusted so that the film thickness after drying was 5 ⁇ m.
- the rotation of the rotating stage corresponds to the solvent weight loss treatment in the first stage.
- the heat treatment (100 ° C.) by the rotating stage was started.
- the second solvent weight loss time T 3 was 120 seconds.
- the heat treatment by the rotary stage corresponds to the solvent weight reduction treatment in the second stage.
- the heat-conducting layer-forming composition was heated and dried until the film thickness of the supplied heat-conducting layer-forming composition was sufficiently stabilized, and then the heat treatment by the rotary stage was completed.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 2 >>> A silicon wafer having a maximum diameter of 150 mm and a straight portion of 47.5 mm on the outer edge was used as the substrate, and the heat conductive layer forming composition Y-1 was used as the heat conductive layer forming composition.
- the rotation of the rotation stage was stopped at the time when the solid content concentration of the heat-conducting layer forming composition reached the first threshold concentration, but in Example 2, the solid content concentration was the first threshold concentration. The feature is that it continued to rotate even after reaching.
- the reference numerals in FIG. 3 are synonymous with the reference numerals in FIG.
- the heat treatment (100 ° C.) by the rotation stage was started.
- the second solvent weight loss time T 3 was 110 seconds.
- the rotation by the rotation stage and the subsequent heat treatment correspond to the solvent weight reduction treatment in the second stage.
- the heat-conducting layer-forming composition was heated and dried until the film thickness of the supplied heat-conducting layer-forming composition was sufficiently stabilized, and then the heat treatment by the rotary stage was completed.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- the heat conductive layer forming composition is exposed to a reduced pressure atmosphere and dried until the film thickness of the supplied heat conductive layer forming composition is sufficiently stabilized, and then the atmosphere inside the processing space of the spin coater is returned to the atmosphere to perform the reduced pressure treatment.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 6 A heat conductive layer was prepared by the same procedure as in Example 1 except that T 2 was set to 300 seconds in relation to the start time of the heat treatment (100 ° C.). The film thickness of the produced heat conductive layer was 5 ⁇ m.
- the silicon wafer was installed on the rotation stage so that the position of the center of gravity of the silicon wafer overlapped with the rotation center of the rotation stage in the horizontal direction, and the rotation stage was set to rotate clockwise (clockwise).
- the heat conductive layer forming composition was discharged from the nozzle of the spin coater toward the position of the center of gravity of the silicon wafer, and the heat conductive layer forming composition was supplied onto the silicon wafer.
- the distance between the nozzle and the support was 25 mm.
- the rotation speed of the rotating stage was quickly increased to 600 rpm, and the state of 600 rpm was maintained for 8 seconds.
- the rotation speed of the rotating stage was quickly increased to 1000 rpm, and the state of 1000 rpm was maintained for 2 seconds.
- the first solvent weight loss time T 1 was 15 seconds.
- the amount of the heat conductive layer forming composition supplied was adjusted so that the film thickness after drying was 5 ⁇ m.
- Example 9 A heat conductive layer was prepared by the same procedure as in Example 1 except that the heat conductive layer forming composition Y-2 was used as the heat conductive layer forming composition.
- the first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 10 seconds and 120 seconds, respectively.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 10 A heat conductive layer was prepared by the same procedure as in Example 1 except that the heat conductive layer forming composition Y-3 was used as the heat conductive layer forming composition and the maximum rotation speed was changed to 700 rpm.
- the first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 30 seconds and 120 seconds, respectively.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 11 A heat conductive layer was prepared by the same procedure as in Example 1 except that the heat conductive layer forming composition Y-4 was used as the heat conductive layer forming composition.
- the first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 10 seconds and 120 seconds, respectively.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 13 A heat conductive layer was prepared by the same procedure as in Example 1 except that the heat conductive layer forming composition Y-6 was used as the heat conductive layer forming composition and the maximum rotation speed was changed to 700 rpm.
- the first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 30 seconds and 120 seconds, respectively.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 14 A heat conductive layer was produced by the same procedure as in Example 1 except that the heat conductive layer forming composition Y-7 was used as the heat conductive layer forming composition.
- the first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 10 seconds and 120 seconds, respectively.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 15 A heat conductive layer was prepared by the same procedure as in Example 1 except that the heat conductive layer forming composition Y-8 was used as the heat conductive layer forming composition.
- the first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 10 seconds and 120 seconds, respectively.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 16 A heat conductive layer was prepared by the same procedure as in Example 1 except that the heat conductive layer forming composition Y-9 was used as the heat conductive layer forming composition and the maximum rotation speed was changed to 500 rpm.
- the first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 120 seconds and 120 seconds, respectively.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 21 When the composition for forming the heat conductive layer was discharged from the nozzle of the spin coater, the heat conductive layer was produced by the same procedure as in Example 1 except that the composition was discharged toward a position 5% away from the position of the center of gravity of the silicon wafer. ..
- the first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 10 seconds and 120 seconds, respectively.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 22 When the composition for forming the heat conductive layer was discharged from the nozzle of the spin coater, the heat conductive layer was produced by the same procedure as in Example 1 except that the composition was discharged toward a position 10% away from the position of the center of gravity of the silicon wafer. ..
- the first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 10 seconds and 120 seconds, respectively.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 23 When the silicon wafer is installed on the rotating stage, the same procedure as in Example 1 is performed, except that the center of rotation of the rotating stage is located 5% horizontally away from the position of the center of gravity of the silicon wafer. A heat-conducting layer was prepared. The first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 10 seconds and 120 seconds, respectively. The film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 24 When the silicon wafer is installed on the rotary stage, the procedure is the same as in the first embodiment except that the center of rotation of the rotary stage is located 10% horizontally away from the center of gravity of the silicon wafer. A heat-conducting layer was prepared. The first solvent weight loss time T 1 and the second solvent weight loss time T 3 were 10 seconds and 120 seconds, respectively. The film thickness of the produced heat conductive layer was 5 ⁇ m.
- the rotation speed of the rotation stage was quickly increased to 1000 rpm, and the state of 1000 rpm was maintained.
- the first solvent weight loss time T 1 was 20 seconds.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 27 A heat conductive layer was produced by the same procedure as in Example 1 except that the rotation direction of the rotation stage of the spin coater was counterclockwise (counterclockwise). At this time, the first solvent weight loss time T 1 was 10 seconds. The film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 28 >>> A heat conductive layer was produced by the same procedure as in Example 1 except that the angular position at the end of rotation of the rotation stage of the spin coater was different from that at the start of rotation. At this time, the first solvent weight loss time T 1 was 10 seconds. The film thickness of the produced heat conductive layer was 5 ⁇ m.
- the heat conductive layer forming composition is discharged toward a position horizontally deviated from the center of gravity of the silicon wafer by 12%, and the heat conductive layer forming composition is placed on the silicon wafer. Supplied.
- the first solvent weight loss time T 1 was 9 seconds.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 17 A silicon wafer having a maximum diameter of 150 mm and a straight portion of 47.5 mm on the outer edge was used as the substrate, and the heat conductive layer forming composition Y-10 was used as the heat conductive layer forming composition.
- the silicon wafer was placed on the fixed stage of the spray coater, and the atmosphere inside the processing space of the spray coater was reduced to 100 Pa. Then, the composition for forming a heat conductive layer was supplied onto the silicon wafer by scanning the nozzle on the silicon wafer at a speed of 5 cm / s while spray-discharging the composition for forming the heat conductive layer from the nozzle of the spray coater. The distance between the nozzle and the support was 50 mm. The amount of the heat conductive layer forming composition supplied was adjusted so that the film thickness after drying was 5 ⁇ m. At this time, the first solvent weight loss time T 1 was 10 seconds. The atmosphere was returned to the atmosphere at the time when the solid content concentration of the heat conductive layer forming composition reached the first threshold concentration.
- the depressurization of the atmosphere inside the treatment space corresponds to the solvent weight reduction treatment in the first stage. After that, no special treatment such as heat treatment was performed, and the composition for forming a heat conductive layer was naturally dried.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 18 A silicon wafer having a maximum diameter of 150 mm and a straight portion of 47.5 mm on the outer edge was used as the substrate, and the heat conductive layer forming composition Y-10 was used as the heat conductive layer forming composition.
- the procedure will be described with reference to FIG.
- the silicon wafer was placed on the fixed stage of the spray coater, and the atmosphere inside the processing space of the spray coater was reduced to 100 Pa.
- the composition for forming a heat conductive layer was supplied onto the silicon wafer by scanning the nozzle on the silicon wafer at a speed of 5 cm / s while spray-discharging the composition for forming the heat conductive layer from the nozzle of the spray coater.
- the distance between the nozzle and the support was 50 mm.
- the amount of the heat conductive layer forming composition supplied was adjusted so that the film thickness after drying was 5 ⁇ m.
- the first solvent weight loss time T 1 was 10 seconds.
- the atmosphere was returned to the atmosphere at the time when the solid content concentration of the heat conductive layer forming composition reached the first threshold concentration.
- the depressurization of the atmosphere inside the treatment space corresponds to the solvent weight reduction treatment in the first stage.
- concentration C C 1
- T 2 300 seconds
- the heat treatment (100 ° C.) by the fixed stage was started.
- the second solvent weight loss time T 3 was 60 seconds.
- the heat-conducting layer-forming composition was heated and dried until the film thickness of the supplied heat-conducting layer-forming composition was sufficiently stabilized, and then the heat treatment by the fixing stage was completed.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 19 A silicon wafer having a maximum diameter of 150 mm and a straight portion of 47.5 mm on the outer edge was used as the substrate, and the heat conductive layer forming composition Y-10 was used as the heat conductive layer forming composition.
- the time chart of this embodiment is also substantially the same as that of Example 17.
- the silicon wafer was installed on the fixed stage of the slit coater, and the atmosphere inside the processing space of the slit coater was reduced to 50 Pa. Then, the composition for forming a heat conductive layer was supplied onto the silicon wafer by scanning the nozzle on the silicon wafer at a speed of 2 cm / s while discharging the composition for forming the heat conductive layer from the nozzle of the slit coater. The distance between the nozzle and the support was 50 ⁇ m. The amount of the heat conductive layer forming composition supplied was adjusted so that the film thickness after drying was 5 ⁇ m. At this time, the first solvent weight loss time T 1 was 10 seconds.
- the atmosphere was returned to the atmosphere at the time when the solid content concentration of the heat conductive layer forming composition reached the first threshold concentration.
- the depressurization of the atmosphere inside the treatment space corresponds to the solvent weight reduction treatment in the first stage. After that, no special treatment such as heat treatment was performed, and the composition for forming a heat conductive layer was naturally dried.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Example 20 A silicon wafer having a maximum diameter of 150 mm and a straight portion of 47.5 mm on the outer edge was used as the substrate, and the heat conductive layer forming composition Y-10 was used as the heat conductive layer forming composition.
- the procedure will be described with reference to FIG.
- those common to the symbols in FIG. 2 have the same meaning as the symbols in FIG. 2, and those common to the symbols in FIG. 3 are the symbols in FIG. It is synonymous with meaning.
- the silicon wafer was installed on the fixed stage of the slit coater, and the atmosphere inside the processing space of the slit coater was reduced to 50 Pa.
- the composition for forming a heat conductive layer was supplied onto the silicon wafer by scanning the nozzle on the silicon wafer at a speed of 2 cm / s while discharging the composition for forming the heat conductive layer from the nozzle of the slit coater.
- the distance between the nozzle and the support was 50 ⁇ m.
- the amount of the heat conductive layer forming composition supplied was adjusted so that the film thickness after drying was 5 ⁇ m.
- the first solvent weight loss time T 1 was 10 seconds.
- the atmosphere was returned to the atmosphere at the time when the solid content concentration of the heat conductive layer forming composition reached the first threshold concentration.
- the depressurization of the atmosphere inside the treatment space corresponds to the solvent weight reduction treatment in the first stage.
- concentration C C 1
- T 2 300 seconds
- the heat treatment (100 ° C.) by the fixed stage was started.
- the second solvent weight loss time T 3 was 60 seconds.
- the heat-conducting layer-forming composition was heated and dried until the film thickness of the supplied heat-conducting layer-forming composition was sufficiently stabilized, and then the heat treatment by the fixing stage was completed.
- the film thickness of the produced heat conductive layer was 5 ⁇ m.
- Each heat conductive layer formed above was patterned by the following method. First, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm is emitted at 250 mJ / cm 2 through a mask having two hole patterns of 50 ⁇ m and 10 ⁇ m in diameter. After irradiation, the heat guide layer was exposed to light. After that, the silicon wafer on which the exposed heat-conducting layer is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and tetramethylammonium hydroxide (TMAH) is placed on the horizontal rotating table. Paddle development was performed at 23 ° C. for 65 seconds using a 0.3 mass% aqueous solution to form a heat-conducting layer in which two hole patterns were formed on each silicon wafer.
- FPA-3000i5 + manufactured by Canon Inc.
- the silicon wafer on which the heat-conducting layer is formed is fixed to a horizontal rotary table by a vacuum chuck method, and while the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, pure water is ejected from above the center of rotation into a shower shape. It was fed, rinsed, and then spray dried. Then, on a hot plate, the heat conductive layer was cured by heating at 200 ° C. for 5 minutes, and then cooled to room temperature.
- Thermal conductivity was evaluated based on thermal diffusivity.
- the thermal diffusivity was measured by a thermal diffusivity measuring device FTC-RT (manufactured by Advanced Riko) based on the periodic heating method (based on ISO 22007-3, the international standard for plastics). It was measured by acquiring reference data of silicon wafers of the same thickness and calculating the difference.
- the thermal diffusivity was measured by bringing the device into contact with the portion where the hole pattern was not formed, and evaluated in the following four stages.
- A: The thermal diffusivity is 1.0 ⁇ 10 -6 m 2 s -1 or more.
- the thermal diffusivity is 5.0 ⁇ 10 -7 m 2 s -1 or more and 1.0 ⁇ 10 -6 m 2 s -1 or less.
- the substrate was changed from a silicon wafer to a substrate in which gold was sputtered on the silicon wafer, and the heat conductive layers according to Examples 1 to 29 and Comparative Example 1 were formed in the same manner as described above.
- the electrical insulation was evaluated based on the volume resistivity of the heat conductive layer on the gold electrode.
- the volume resistivity was measured using a High Restor-UX MCP-HT800 (based on JIS K6911) as a resistivity meter for high resistance, and evaluated in the following four stages.
- A 1.0 x 10 12 ⁇ ⁇ cm or more.
- B 1.0 ⁇ 10 11 ⁇ ⁇ cm or more and less than 1.0 ⁇ 10 12 ⁇ ⁇ cm.
- C 1.0 ⁇ 10 10 ⁇ ⁇ cm or more and less than 1.0 ⁇ 10 11 ⁇ ⁇ cm.
- D 1.0 ⁇ 10 less than 10 ⁇ ⁇ cm.
- ⁇ Plane The heat-conducting layer after drying according to each example was cured by irradiating the heat-conducting layer with ultraviolet rays at an exposure amount of 3000 mJ / cm 2 using an ultraviolet photoresist curing device (UMA-802-HC-552, manufactured by Ushio Denki Co., Ltd.). A film was formed. Next, this cured film is lined so as to pass through the center, and using a contact type film thickness meter (Dektake XT, Bruker), the thinnest part (center part) and the thickest part (peripheral part) of the film thickness. The film thickness of was measured. The surface condition was evaluated by the difference between these measured values. It can be said that the smaller the difference, the higher the flatness.
- A The difference in film thickness is 0.1 ⁇ m or less.
- B The difference in film thickness is larger than 0.1 ⁇ m and 0.25 ⁇ m or less.
- C The difference in film thickness is larger than 0.25 ⁇ m and 0.5 ⁇ m or less.
- D The difference in film thickness is larger than 0.5 ⁇ m.
- Example 29 As the support, "heat conductive sheet iCas KR manufactured by Tomoegawa Paper Co., Ltd.” was cut into a disk shape, and the rotation speed in the latter half (1000 rpm in Example 1) was changed to 600 rpm by the same procedure as in Example 1. , A heat conductive layer was prepared. As the heat conductive layer forming composition, the heat conductive layer forming composition Y-1 was used. After that, as in Example 1, thermal conductivity was carried out by the same method as in Example 1 except that the heat conductive layer was not patterned and cured by the method described in the above " ⁇ Pattern formation>". , Electrical insulation and surface shape were evaluated.
- thermo conductivity The evaluation results are described in the columns of “thermal conductivity”, “insulation”, and “plane” in the table below, respectively.
- thermal resistance evaluation and “die shear strength evaluation” were performed by the methods described later, and the evaluation results are described in the columns of “thermal resistance” and “die shear strength” in the table below, respectively.
- Example 30 Using the support A obtained by the following method as the support, a heat conductive layer was prepared by the same procedure as in Example 1 except that the rotation speed in the latter half (1000 rpm in Example 1) was changed to 600 rpm.
- the heat conductive layer forming composition As the heat conductive layer forming composition, the heat conductive layer forming composition Y-1 was used.
- thermal conductivity was carried out by the same method as in Example 1 except that the heat conductive layer was not patterned and cured by the method described in the above " ⁇ Pattern formation>”.
- Electrical insulation and surface shape were evaluated. The evaluation results are described in the columns of "thermal conductivity”, “insulation”, and “plane” in the table below, respectively.
- thermal resistance evaluation” and “die shear strength evaluation” were performed by the methods described later, and the evaluation results are described in the columns of “thermal resistance” and “die shear strength” in the table below, respectively.
- the total content of the mixture and triphenylphosphine in the composition was set so that the total content (mass%) with respect to the total solid content in the composition was 18.6% by mass.
- the content of the boron nitride particles in the composition is such that the total content (% by volume) with respect to the total solid content in the composition is 68.0% by volume (the total content (mass%) with respect to the total solid content is 81. (Amount to be 4% by mass).
- the composition for forming a support was uniformly applied onto the release surface of the release-treated polyester film using an applicator, and left at 120 ° C. for 5 minutes to obtain a coating film. The coating amount was such that the film thickness after drying was 290 ⁇ m.
- a new polyester film is further laminated on the coating film of the film with a coating film thus obtained so that the release surfaces face each other to form a "polyester film-coating film-polyester film” configuration.
- a laminate having was obtained. The laminate was roll-pressed. The laminate after the roll press was treated with a hot press under air (hot plate temperature 180 ° C., pressure 20 MPa for 5 minutes, and then further treated at normal pressure at 180 ° C. for 90 minutes). The polyester films on both sides of the laminated body were peeled off, and the remaining layer was cut into a disk shape to obtain a support A (average film thickness 200 ⁇ m).
- a heat conductive layer (heat conductive layer 2) was formed on the aluminum wafer by the same method as in each example.
- the side of the support on which the heat-conducting layer (heat-conducting layer 1) manufactured in each embodiment is formed on the heat-conducting layer (heat-conducting layer 2) formed on the obtained aluminum wafer, which is not in contact with the heat-conducting layer. Faces were brought into contact.
- a 3 mm square test chip manufactured by Cima Electronics Co., Ltd.
- a built-in heater and temperature sensor is placed on the upper surface of the heat conductive layer (heat conductive layer 1) formed on the support, and the pressure at 140 ° C. for 2 minutes at the time of joining.
- the test chip and the support were bonded via the heat conductive layer 1, and the support and the aluminum wafer were bonded via the heat conductive layer 2.
- This joining was performed using a chip bonder (DB250, manufactured by Shibuya Kogyo Co., Ltd.). Then, it was heated at 175 ° C. for 2 hours to obtain a laminate. With the temperature of the cooling plate controlled to 25 ° C., the power supply voltage and current were adjusted so that the output of the heater was 10 W, the chip temperature, ambient temperature, and power consumption were measured, and the thermal resistance was calculated.
- the evaluation criteria are as follows. A: The thermal resistance is less than 3.0 K / W.
- B Thermal resistance is 3.0 K / W or more.
- Die-share strength evaluation >>> After the thermal resistance was measured, the laminate was subjected to a die shear test using a universal bond tester (manufactured by DAGE4000 DAGE), and the adhesive strength was measured.
- the evaluation criteria are as follows. A: The adhesive strength is 10 MPa or more. B: Adhesive strength is less than 10 MPa.
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Abstract
Description
<1>
樹脂、フィラーおよび溶剤を含みかつ固形分濃度が90質量%未満である導熱層形成用組成物を用いて、熱拡散率が3.0×10-7m2s-1以上である導熱層を支持体上に製造する製造方法であって、
導熱層形成用組成物を支持体に向けて吐出する吐出工程、および、
支持体上の位置ごとに、導熱層形成用組成物が吐出されてから導熱層形成用組成物中の固形分濃度が支持体上で90質量%に至るまでの第1の溶剤減量時間が10秒以上となるように、導熱層形成用組成物中の溶剤を減量する溶剤減量工程を含む、導熱層の製造方法。
<2>
第1の溶剤減量時間が、120秒以下である、
<1>に記載の導熱層の製造方法。
<3>
上記溶剤減量工程において、導熱層形成用組成物中の固形分濃度が90質量%を超えた支持体上の位置に対し、雰囲気の減圧および支持体の加熱の少なくとも1種の溶剤減量処理を行う、
<1>または<2>に記載の導熱層の製造方法。
<4>
支持体上の位置ごとに、導熱層形成用組成物中の固形分濃度が支持体上で90質量%を超えてから溶剤減量処理が開始されるまでの時間が、60秒以下である、
<3>に記載の導熱層の製造方法。
<5>
支持体上の位置ごとに、導熱層形成用組成物中の固形分濃度が、支持体上で90質量%を超えてから、さらなる溶剤の減量により99質量%に至るまでの第2の溶剤減量時間が、60~300秒である、
<3>または<4>に記載の導熱層の製造方法。
<6>
樹脂、フィラーおよび溶剤を含む導熱層形成用組成物を用いて、熱拡散率が3.0×10-7m2s-1以上である導熱層を支持体上に製造する製造方法であって、
スピンコート法により導熱層形成用組成物を支持体上に適用する適用工程を含み、
上記適用工程において導熱層形成用組成物を支持体上に供給する際に、支持体の適用面における重心を中心とし、かつ、重心とこの重心から最も離れた適用面上の点とをそれぞれ末端とする線分の長さの10%の長さを半径とする円領域に、導熱層形成用組成物を供給する、導熱層の製造方法。
<7>
導熱層形成用組成物が上記円領域に供給される前に支持体を回転させる、
<6>に記載の導熱層の製造方法。
<8>
上記適用工程において、支持体の回転速度を変更する、
<6>または<7>に記載の導熱層の製造方法。
<9>
上記適用工程において、支持体の回転方向が時計回りである、
<6>~<8>のいずれか1つに記載の導熱層の製造方法。
<10>
上記適用工程において、支持体の回転終了時に、支持体の回転方向への角度位置を回転開始時と同じ角度位置に調整する、
<6>~<9>のいずれか1つに記載の導熱層の製造方法。
<11>
支持体上に供給する前の導熱層形成用組成物の固形分濃度が90質量%未満であり、
適用工程が、導熱層形成用組成物を支持体に向けて吐出する吐出工程を含み、
支持体上の位置ごとに、導熱層形成用組成物が吐出されてから導熱層形成用組成物中の固形分濃度が支持体上で90質量%に至るまでの第1の溶剤減量時間が10秒以上となるように、支持体を回転させる、
<6>~<10>のいずれか1つに記載の導熱層の製造方法。
<12>
フィラーの平均一次粒子径が10μm以下である、
<1>~<11>のいずれか1つに記載の導熱層の製造方法。
<13>
フィラーの含有量が、導熱層形成用組成物中の全固形分量に対し50~75体積%である、
<1>~<12>のいずれか1つに記載の導熱層の製造方法。
<14>
<1>~<13>のいずれか1つに記載の導熱層の製造方法により、支持体上に導熱層を製造することを含む、支持体および導熱層を含む積層体の製造方法。
<15>
<1>~<13>のいずれか1つに記載の導熱層の製造方法により、支持体上に導熱層を製造することを含む、支持体および導熱層を含む半導体デバイスの製造方法。
本明細書において、「常圧」とは101.325kPaである。
第1の態様における本発明の導熱層の製造方法は、樹脂、フィラーおよび溶剤を含みかつ固形分濃度が90質量%未満である導熱層形成用組成物を用いて、熱拡散率が3.0×10-7m2s-1以上である導熱層を支持体上に製造する製造方法である。そして、導熱層の製造方法は、導熱層形成用組成物を支持体に向けて吐出する吐出工程、および、支持体上の位置ごとに、導熱層形成用組成物が吐出されてから導熱層形成用組成物中の固形分濃度が支持体上で90質量%(以下、「第1閾値濃度」ともいう。)に至るまでの第1の溶剤減量時間が10秒以上となるように、導熱層形成用組成物中の溶剤を減量する溶剤減量工程を含む。
以下、本発明の導熱層の製造方法について詳細に説明する。本発明の導熱層の製造方法は、上記のとおり、熱拡散率が3.0×10-7m2s-1以上である導熱層を支持体上に製造する方法である。このような導熱層は、優れた熱伝導性および電気絶縁性を有するため、LSIデバイスなどの半導体デバイス用の放熱用樹脂絶縁層として好適に使用できる。導熱層は、例えば、少なくとも1種のフィラーと樹脂と溶剤とを含有する組成物を基材上に適用し、その膜を乾燥させたり硬化させたりすることにより形成できる。このとき、例えば図1に示すように、本発明の導熱層4は、基材1上に形成された樹脂膜2中にフィラー3が分散した構造を有する。導熱層4は、フィラー3を含有し、かつ、3.0×10-7m2s-1以上という熱拡散率を有することで、高い熱伝導性を発現する。そのため、導熱層4に伝わった熱エネルギーEは、特にフィラー3が存在する領域を伝達しながら、反対側から速やかに放出される。また、導熱層は、適用する半導体デバイスに応じて、パターン形状を有することもできる。
<<<吐出工程>>>
第1の態様における導熱層の製造方法において、吐出工程は、ノズル等の供給手段から導熱層形成用組成物を支持体上に向けて供給する工程である。導熱層形成用組成物の供給手段は、導熱層形成用組成物の支持体への適用方法に応じて適宜決められる。
第1の態様における導熱層の製造方法において、溶剤減量工程は、上記のとおり、支持体上の位置ごとに、第1の溶剤減量時間が10秒以上となるように、導熱層形成用組成物中の溶剤を減量する工程である。すなわち、溶剤減量工程は、供給前の固形分濃度が90質量%未満である導熱層形成用組成物の固形分濃度が支持体上で第1閾値濃度に至るまでの時間を制御する工程と言える。これにより、導熱層の熱伝導性および電気絶縁性が適切に発揮される。ここで、「減量」には、揮発等により溶剤のみを分離して減らすこと、および、導熱層形成用組成物の一部を取り除く等により、溶剤と他の成分とを一緒に減らすことの両方の意味が含まれる。また、第1の溶剤減量時間の開始時点は、上記のとおり、導熱層形成用組成物が吐出されたとき、すなわち、導熱層形成用組成物が外気に曝されたときである。
第2の態様の導熱層の製造方法において、支持体の適用面における重心は、適用面へ投影された支持体の重心を意味し、適用面を平面として扱った際の幾何学的な質量中心ともいえる。支持体の重心位置は、公知の方法で求めることができ、幾何学的な計算によって求めてもよく、支持体を裏面から支えることができる一点を探す方法で求めてもよい。そして、導熱層形成用組成物を適用する適用面における重心を中心とし、かつ、上記重心と上記重心から最も離れた適用面上の点とをそれぞれ末端とする線分の長さの10%の長さを半径とする円領域(円の内側領域も含む。)に、導熱層形成用組成物を供給する。これにより、導熱層の熱伝導性および電気絶縁性が適切に発揮される。なお、導熱層形成用組成物を供給したあと、組成物の一部が上記円領域の外側に流出してもよい。さらに、導熱層形成用組成物を供給する円領域は、適用面における重心を中心とする円領域のなかでも、上記線分の長さの8%の長さを半径とする円領域であることがより好ましく、上記線分の長さの5%の長さを半径とする円領域であることがさらに好ましい。
本発明の導熱層の製造方法の具体例1について、タイムチャートを示しながら説明する。図2は、支持体上の所定の位置における固形分濃度や溶剤減量処理の時間的関係を示すタイムチャートである。特に、本具体例では、スピンコート法により導熱層形成用組成物を支持体上に適用する場合の例である。なお、図中のタイムチャートの縮尺は、便宜上、適宜変更しており、実際の時間軸と必ずしも一致しない。図2中の符号の意味は下記のとおりである。
・実線A:導熱層形成用組成物の固形分濃度。
・濃度C1:第1閾値濃度(90質量%)
・濃度C2:第2閾値濃度(99質量%)
・段階ST1:導熱層形成用組成物の固形分濃度が第1閾値濃度に至るまでの段階(第1段階)。
・段階ST2:導熱層形成用組成物の固形分濃度が第1閾値濃度に至った後の段階(第2段階)。
・1点鎖線B:回転ステージの回転速度。
・時刻ta:回転ステージの回転開始時刻。
・時刻tb:回転ステージの回転終了時刻。
・ハッチング領域D:第2段階での溶剤減量処理(加熱)の実施期間。
・時刻td:第2段階での溶剤減量処理の開始時刻。
・時刻t1:導熱層形成用組成物のウェハへの吐出時刻。
・時刻t2:導熱層形成用組成物の固形分濃度が第1閾値濃度に至った時刻。
・時刻t3:導熱層形成用組成物の固形分濃度が第2閾値濃度に至った時刻。
・期間T1:導熱層形成用組成物が時刻t=t1にて吐出されてから、導熱層形成用組成物の固形分濃度が時刻t=t2にて第1閾値濃度(濃度C=C1)に至るまでの時間(第1の溶剤減量時間)。
・期間T2:導熱層形成用組成物の固形分濃度が時刻t=t2にて第1閾値濃度(濃度C=C1)に至ってから、第2段階での溶剤減量処理が時刻t=tdにて開始されるまでの時間。
・期間T3:導熱層形成用組成物の固形分濃度が時刻t=t2にて第1閾値濃度(濃度C=C1)に至ってから、導熱層形成用組成物の固形分濃度が時刻t=t3にて第2閾値濃度(濃度C=C2)に至るまでの時間(第2の溶剤減量時間)。
本発明の導熱層の製造方法の具体例2について、タイムチャートを示しながら説明する。図4は、支持体上の所定の位置における固形分濃度や溶剤減量処理の時間的関係を示すタイムチャートである。特に、本具体例では、スプレーコート法により導熱層形成用組成物を支持体上に適用する場合の例である。なお、図4中の新たな符号の意味は下記のとおりである。また、図4中の符号のうち、図2中の符号と共通するものは、図2中の符号と同義である。
・ハッチング領域D1:溶剤減量処理(減圧)の実施期間。
・ハッチング領域D2:溶剤減量処理(加熱)の実施期間。
本発明の導熱層の製造方法の具体例4について、タイムチャートを示しながら説明する。図5は、支持体上の所定の位置における固形分濃度や溶剤減量処理の時間的関係を示すタイムチャートである。特に、本具体例では、スリットコート法により減圧雰囲気の中で導熱層形成用組成物を支持体上に適用し、さらに第2段階において追加の加熱処理を実施する場合の例である。なお、図5中の符号のうち、図2中の符号と共通するものは、図2中の符号の意味と同義であり、図4中の符号と共通するものは、図4中の符号の意味と同義である。
以下、導熱層形成用組成物の各成分について説明する。
本発明の組成物は、フィラーを含む。フィラーは、熱伝導性であることが好ましい。フィラーは電気絶縁性であっても、半導体や導電性であってもよい。電気絶縁性および導電性の程度は、設計や目的に応じて、適宜選択される。例えば、電気絶縁性フィラーの場合には、そのフィラーの体積抵抗率の下限は、1.0×1011Ω・cm以上であることが好ましく、3.0×1011Ω・cm以上であることがより好ましく、1.0×1012Ω・cm以上であることが特に好ましい。また、体積抵抗率の上限は、特に限定されないが、実用的には1.0×1018Ω・cmである。
また、少なくとも2つのピークの間について、粒度の小さいピークに対する粒度の大きいピークのピーク強度比は、0.2~5.0であることが好ましい。下限は、0.2以上であることが好ましく、0.5以上であることがより好ましい。上限は、5.0以下であることが好ましく、3.0以下であることがより好ましい。
組成物の全固形分の体積に対するフィラーの含有量は、溶剤減量工程後の導熱層において、導熱層の体積に占めるフィラーの体積の割合として算出される。上記各体積の算出は、23℃の条件下で行われる。
本発明の導熱層の製造に使用される樹脂は、例えば、フィラー同士を結合させる用途で使用するバインダー、フィラーを組成物中で分散させる用途で使用する分散剤、絶縁層を形成する用途で使用する重合性化合物、および、重合性化合物の重合反応を促進させる用途で使用される重合促進剤などを含有してもよい。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で使用することもできる。樹脂は、ポリイミド樹脂、アクリル樹脂、および、エポキシ樹脂のうち少なくとも1種を含むことが好ましい。以下、樹脂について詳細に説明する。
aは、各々独立に、1~5の整数を表す。なお、本明細書において、*(アスタリスク)は繰り返し単位間の連結部を表す。
R8およびR9は、それぞれ独立に、R1と同義の基である。
Lは、単結合、アルキレン基(炭素数1~6が好ましい)、アルケニレン基(炭素数2~6が好ましい)、アリーレン基(炭素数6~24が好ましい)、ヘテロアリーレン基(炭素数1~6が好ましい)、イミノ基(炭素数0~6が好ましい)、エーテル基、チオエーテル基、カルボニル基、および、これらの組合せに係る連結基である。なかでも、単結合または-CR5R6-NR7-(イミノ基がXまたはYの方になる)であることが好ましい。
ここで、R5およびR6は、各々独立に、水素原子、ハロゲン原子、アルキル基(炭素数1~6が好ましい)を表す。R7は、水素原子または炭素数1~6のアルキル基である。
Laは、CR8CR9とN原子とともに環構造を形成する構造部位である。そして、Laは、CR8CR9の炭素原子と合わせて炭素数3~7の非芳香族複素環を形成する構造部位であることが好ましい。より好ましくは、Laは、CR8CR9の炭素原子およびN原子(窒素原子)を合わせて5~7員の非芳香族複素環を形成する構造部位である。さらに好ましくは、Laは、5員の非芳香族複素環を形成する構造部位であり、ピロリジンを形成する構造部位であることが特に好ましい。Laは、さらにアルキル基等の置換基を有していてもよい。
Xは、pKa14以下の官能基を有する基を表す。
Yは、原子数40~10,000のオリゴマー鎖またはポリマー鎖を表す。
Yaは、アニオン基を有する原子数40~10,000のオリゴマー鎖またはポリマー鎖を表す。
本発明の導熱層の製造に使用される組成物は、重合性化合物を含有することが好ましい。重合性化合物としては、少なくとも1個のエチレン性不飽和二重結合を有する化合物が好ましく、末端エチレン性不飽和結合を少なくとも1個、好ましくは2個以上有する化合物がより好ましい。また、重合性化合物は、エチレン性不飽和二重結合を6個以上有する化合物であるか、エチレン性不飽和二重結合を3~4個有する化合物であることが好ましく、エチレン性不飽和二重結合を3~4個有する化合物であることがさらに好ましい。エチレン性不飽和結合を有する基は、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基であることが好ましい。また、重合性化合物は、ラジカル重合性化合物であることが好ましい。また、重合性化合物は、ヒドロキシメチル基およびアルコキシメチル基からなる群から選ばれる少なくとも1つを分子内に2個以上有する化合物を含有することが好ましい。アルコキシメチル基中のアルキル鎖の炭素数は、1~10であることが好ましく、1~5であることがより好ましく、1または2であることがさらに好ましい。つまり、アルコキシメチル基は、メトキシメチル基またはエトキシメチル基であることが好ましい。
本発明の導熱層の製造に使用される組成物は、架橋剤を含有することが好ましい。好ましい架橋剤としては、ヒドロキシメチル化またはアルコキシメチル化系フェノール化合物、アルコキシメチル化メラミン系化合物、アルコキシメチルグリコールウリル系化合物類およびアルコキシメチル化ウレア系化合物が挙げられ、その中でもヒドロキシメチル化またはアルコキシメチル化系フェノール化合物が、良好なパターン形状が得られることからより好ましい。特に好ましい架橋剤としては、分子内にベンゼン環を3~5個含み、さらにヒドロキシメチル基およびアルコキシメチル基からなる群から選ばれる少なくとも1種を2個以上有し、分子量が1200以下のフェノール誘導体や、少なくとも2個の遊離N-アルコキシメチル基を有するメラミン-ホルムアルデヒド誘導体やアルコキシメチルグリコールウリル誘導体が挙げられる。
本発明の導熱層の製造に使用される組成物は光重合開始剤を含有することが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線、活性光線または放射線に対して感光性を有する化合物が好ましい。特に、光重合開始剤は、光ラジカル重合開始剤、または、活性光線もしくは放射線の照射により酸を発生する化合物が好ましい。また、光重合開始剤は、約300nm~800nm(330nm~500nmがより好ましい。)の範囲内に少なくとも約50のモル吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。
本発明の導熱層の製造に使用される組成物は、光重合開始剤として、活性光線または放射線の照射により酸を発生する化合物(以下、単に「酸発生剤」ともいう。)を含有していてもよい。
本発明の導熱層の製造に使用される組成物は、溶剤を含有することが好ましい。溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、アルコール類、エステル類、エーテル類、ケトン類、芳香族炭化水素類、スルホキシド類、アミド類などの化合物が挙げられる。
本発明の導熱層の製造に使用される組成物は、密着剤を含有することができ、密着剤は、例えば、シランカップリング剤である。この態様によれば、ウェハ等の基材や金属配線等下地と膜との密着性を向上させることができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応および/または縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基は、樹脂との間で相互作用するかもしくは結合を形成して親和性を示す基が好ましい。例えば、(メタ)アクリロイル基、フェニル基、メルカプト基、エポキシ基、オキセタニル基が挙げられ、(メタ)アクリロイル基およびエポキシ基が好ましい。即ち、シランカップリング剤は、アルコキシシリル基と、(メタ)アクリロイル基および/またはエポキシ基とを有する化合物が好ましく、アルコキシシリル基と、(メタ)アクリロイル基とを有する化合物がより好ましい。
本発明の導熱層の製造に使用される組成物は、さらに共増感剤を含有することも好ましい。共増感剤は、光重合開始剤や増感剤の活性放射線に対する感度を一層向上させたり、酸素による重合性化合物の重合阻害を抑制したりするなどの作用を有する。共増感剤について、例えば、特開2010-106268号公報の段落0254~0257(対応する米国特許出願公開第2011/0124824号明細書の<0277>~<0279>)の説明を参酌でき、これらの内容は本明細書に組み込まれる。
本発明の導熱層の製造に使用される組成物は、組成物の製造中あるいは保存中において重合可能なエチレン性不飽和二重結合を有する化合物(例えば、重合性化合物など)の不要な重合を阻止するために、重合禁止剤を含有することが好ましい。
フェノール系水酸基含有化合物(好ましくは、ハイドロキノン、4-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチル-4-メチルフェノール(BHT)、フェノール樹脂類、およびクレゾール樹脂類からなる群より選択される化合物);
N-オキシド化合物類(好ましくは、5,5-ジメチル-1-ピロリンN-オキシド、4-メチルモルホリンN-オキシド、ピリジンN-オキシド、4-ニトロピリジンN-オキシド、3-ヒドロキシピリジンN-オキシド、ピコリン酸N-オキシド、ニコチン酸N-オキシド、およびイソニコチン酸N-オキシドからなる群より選択される化合物);
ピペリジン1-オキシルフリーラジカル化合物類(好ましくは、ピペリジン1-オキシルフリーラジカル、2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカル、4-オキソ-2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカル、4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシルフリーラジカル、4-アセトアミド-2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカル、4-マレイミド-2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカル、および4-ホスホノオキシ-2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカルからなる群より選択される化合物);
ピロリジン1-オキシルフリーラジカル化合物類(好ましくは、3-カルボキシプロキシルフリーラジカル(3-カルボキシ-2,2,5,5-テトラメチルピロリジン1-オキシルフリーラジカル));
N-ニトロソフェニルヒドロキシルアミン類(好ましくは、N-ニトロソフェニルヒドロキシルアミン第一セリウム塩およびN-ニトロソフェニルヒドロキシルアミンアルミニウム塩からなる化合物群から選択される化合物);
ジアゾニウム化合物類(好ましくは、4-ジアゾフェニルジメチルアミンの硫酸水素塩、4-ジアゾジフェニルアミンのテトラフルオロホウ酸塩、および3-メトキシ-4-ジアゾジフェニルアミンのヘキサフルオロリン酸塩からなる群より選択される化合物);
カチオン染料類;
スルフィド基含有化合物類;
ニトロ基含有化合物類;
FeCl3、CuCl2などの遷移金属化合物類。
本発明の導熱層の製造に使用される組成物は、塗布性をより向上させる観点から、各種の界面活性剤を含有してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。
本発明の導熱層の製造に使用される組成物は、紫外線吸収剤を含有してもよい。紫外線吸収剤は、共役ジエン系化合物が好ましく、下記式(I)で表される化合物がより好ましい。
本発明の組成物は、さらにマイグレーション抑制剤を含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層(金属配線)由来の金属イオンが膜内へ移動することを効果的に抑制可能となる。
本発明の組成物は、硬化促進剤を含んでいてもよい。硬化促進剤は、熱硬化促進剤でも光硬化促進剤でもよい。組成物がポリイミド前駆体を含有する場合には、硬化促進剤は、熱硬化促進剤が好ましい。熱硬化促進剤は、加熱により塩基を発生するものであることが好ましい。このような熱硬化促進剤は、例えば、下記の化合物であることが好ましい。
さらに、組成物は、硬化皮膜の物性を改良するために、可塑剤および感脂化剤等の公知の添加剤を含有してもよい。可塑剤は、例えば、ジオクチルフタレート、ジドデシルフタレート、トリエチレングリコールジカプリレート、ジメチルグリコールフタレート、トリクレジルホスフェート、ジオクチルアジペート、ジブチルセバケート、トリアセチルグリセリン等である。可塑剤の含有量は、重合性化合物と樹脂との合計質量に対し10質量%以下であることが好ましい。可塑剤の市販品としては、例えばO-180A(ADEKA製)を使用できる。
上述の組成物は、前述の成分を混合して調製できる。
本発明の積層体5は、図1に示すとおり、基材1と、この基材1上に形成された本発明の導熱層4或いは乾燥膜とを有する。この積層体は、導熱層に接する吸熱部をさらに有してもよい。吸熱部は、冷却モジュールであり、例えば、放熱フィン、ヒートパイプ、ペルチェモジュール、クーリングプレートなどである。
ニホンハンダ(株)製 商品名:ドーデント 型番 NH-070A(L)
スリーボンド(株)製 商品名:3300シリーズ 型番 380B 二液型エポキシ系導電接着剤
下記表1に示した配合比(質量部)となるように各材料を配合し、混合した。そして、この混合物に対して、循環型分散装置(ビーズミル)を用いて下記の条件で分散処理を実施し、分散液X-1からX-5を調製した。
分散処理の条件
・ビーズ材:ジルコニア
・ビーズ径:直径0.2mm
・ビーズ充填率:65体積%
・周速:6m/秒
・ポンプ供給量:10.8kg/時間
・冷却水:水道水
・ビーズミル環状通路内容積:0.15L
・分散処理する混合液量:0.65kg
・L-1:アルミナ(平均一次粒子径3μm、アスペクト比1)。住友化学社製、スミコランダムAA-3。
・L-2:アルミナ(平均一次粒子径0.7μm、アスペクト比1)。住友化学社製、スミコランダムAA-07。
・M-1:アルミナ(平均一次粒子径0.4μm、アスペクト比1)。住友化学社製、スミコランダムAA-04。
・M-2:アルミナ(平均一次粒子径0.3μm、アスペクト比1)。住友化学社製、スミコランダムAA-03F。
・N-1:下記構造の樹脂(Mw=13000)。各繰り返し単位に併記した数値は、各繰り返し単位の含有量(モル比)を表す。側鎖の繰り返し部位に併記される数値は、側鎖の繰り返し部位の繰り返し数を示す。
・N-2:下記構造の樹脂(Mw=13000)。各繰り返し単位に併記した数値は、各繰り返し単位の含有量(モル比)を表す。側鎖の繰り返し部位に併記される数値は、側鎖の繰り返し部位の繰り返し数を示す。
・U-1:プロピレングリコールモノメチルエーテルアセテート(PGMEA)
・U-2:シクロペンタノン
下記表2に示した配合比(質量部)となるように各材料を配合し、混合した。そして、孔径20~30μmのポリテトラフルオロエチレン(PTFE)製メンブレンフィルタ(ウインテック社製)を使用し、上記混合物を濾過することにより、導熱層形成用組成物Y-1からY-9を調整した。
・A-1:下記構造の樹脂(Mw=30000)。各繰り返し単位に併記した数値は、各繰り返し単位の含有量(モル比)を表す。
・A-2:ポリ(パラヒドロキシスチレン)(Mw=4000)。
・B-1:エポキシ樹脂。三菱ケミカル社製、jER1031S。
・B-2:エポキシ樹脂。三菱ケミカル社製、YX7700。
・B-3:下記構造の化合物。
・C-1:2-メチルナフト[2,1-b]フラン-1(2H)-オンO-トシルオキシム。
・C-2:N-シクロヘキシルカルバミン酸9-アントリルメチル。富士フイルム和光純薬社製、WPBG-041。
X-1からX-5はそれぞれ、上記で調製した分散液X-1からX-5である。
・H-1:プロピレングリコールモノメチルエーテルアセテート(PGMEA)
・H-2:シクロペンタノン
上記で調製した導熱層形成用組成物Y-1からY-9を用いて、スピンコート法、スプレーコート法またはスリットコート法により下記の手順で導熱層を作製した。
<<<実施例1>>>
基板(支持体)として直径の最大値が150mmで外縁に47.5mmの直線部を有するシリコンウェハを使用し、導熱層形成用組成物として導熱層形成用組成物Y-1を使用した。以下、図2を参照しながら手順を説明する。なお、図2中の符号の意味は下記のとおりである。
・実線A:導熱層形成用組成物の固形分濃度。
・濃度C1:第1閾値濃度(90質量%)
・濃度C2:第2閾値濃度(99質量%)
・段階ST1:導熱層形成用組成物の固形分濃度が第1閾値濃度に至るまでの段階(第1段階)。
・段階ST2:導熱層形成用組成物の固形分濃度が第1閾値濃度に至った後の段階(第2段階)。
・1点鎖線B:回転ステージの回転速度。
・時刻ta:回転ステージの回転開始時刻。
・時刻tb:回転ステージの回転終了時刻。
・ハッチング領域D:第2段階での溶剤減量処理の実施期間。
・時刻td:第2段階での溶剤減量処理の開始時刻。
・時刻t1:導熱層形成用組成物のウェハへの吐出時刻。
・時刻t2:導熱層形成用組成物の固形分濃度が第1閾値濃度に至った時刻。
・時刻t3:導熱層形成用組成物の固形分濃度が第2閾値濃度に至った時刻。
・期間T1:導熱層形成用組成物が時刻t=t1にて吐出されてから、導熱層形成用組成物の固形分濃度が時刻t=t2にて第1閾値濃度(濃度C=C1)に至るまでの時間(第1の溶剤減量時間)。
・期間T2:導熱層形成用組成物の固形分濃度が時刻t=t2にて第1閾値濃度(濃度C=C1)に至ってから、第2段階での溶剤減量処理が時刻t=tdにて開始されるまでの時間。
・期間T3:導熱層形成用組成物の固形分濃度が時刻t=t2にて第1閾値濃度(濃度C=C1)に至ってから、導熱層形成用組成物の固形分濃度が時刻t=t3にて第2閾値濃度(濃度C=C2)に至るまでの時間(第2の溶剤減量時間)。
基板として直径の最大値が150mmで外縁に47.5mmの直線部を有するシリコンウェハを使用し、導熱層形成用組成物として導熱層形成用組成物Y-1を使用した。実施例1では、導熱層形成用組成物の固形分濃度が第1閾値濃度に至った時刻に合わせて、回転ステージの回転を止めたが、実施例2では、固形分濃度が第1閾値濃度に至った後も回転を継続した点が特徴である。以下、図3を参照しながら手順を説明する。なお、図3中の符号は、図2中の符号と同義である。
実施例3において、導熱層形成用組成物の固形分濃度が第1閾値濃度(濃度C=C1)に至った後、110秒間、回転を継続した点以外は、実施例2と同様に実施した。すなわち、実施例3においては、固形分濃度が第1閾値濃度(濃度C=C1)に至った後、110秒間、回転を継続し、回転ステージの回転速度を1000rpmから減少させ始めたときから60秒後に(時刻t=td、T2=170秒)、回転ステージによる加熱処理(100℃)を開始した。第2の溶剤減量時間T3は90秒であった。
実施例4において、導熱層形成用組成物の固形分濃度が第1閾値濃度(濃度C=C1)に至った後、290秒間、回転を継続した点以外は、実施例2と同様に実施した。すなわち、実施例4においては、固形分濃度が第1閾値濃度(濃度C=C1)に至った後、290秒間、回転を継続し、回転ステージの回転速度を1000rpmから減少させ始めたときから60秒後に(時刻t=td、T2=350秒)、回転ステージによる加熱処理(100℃)を開始した。第2の溶剤減量時間T3は60秒であった。
実施例5は、特に、第2段階での溶剤減量処理として減圧処理(100Pa)を採用した点で、実施例1と異なる。具体的には次のとおりである。
加熱処理(100℃)の開始時刻に関連して、T2を300秒にした点以外は、実施例1と同様の手順により、導熱層を作製した。作製された導熱層の膜厚は5μmであった。
T3=300秒となるように第2段階での加熱温度を下げた点以外は、実施例1と同様の手順により、導熱層を作製した。このとき、第1の溶剤減量時間T1は10秒であった。作製された導熱層の膜厚は5μmであった。
実施例8は、特に、回転ステージの回転速度を上昇させる途中に回転速度を600rpmで維持する工程を設けた点で、実施例1と異なる。具体的には次のとおりである。
導熱層形成用組成物として導熱層形成用組成物Y-2を使用した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ10秒および120秒であった。作製された導熱層の膜厚は5μmであった。
導熱層形成用組成物として導熱層形成用組成物Y-3を使用し、かつ、最大回転速度を700rpmに変更した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ30秒および120秒であった。なお、回転速度を減少させるタイミングも、実施例1と同様に、固形分濃度が第1閾値濃度(濃度C=C1)に至った時刻に合わせた。作製された導熱層の膜厚は5μmであった。
導熱層形成用組成物として導熱層形成用組成物Y-4を使用した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ10秒および120秒であった。作製された導熱層の膜厚は5μmであった。
導熱層形成用組成物として導熱層形成用組成物Y-5を使用した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ10秒および120秒であった。作製された導熱層の膜厚は5μmであった。
導熱層形成用組成物として導熱層形成用組成物Y-6を使用し、かつ、最大回転速度を700rpmに変更した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ30秒および120秒であった。なお、回転速度を減少させるタイミングも、実施例1と同様に、固形分濃度が第1閾値濃度(濃度C=C1)に至った時刻に合わせた。作製された導熱層の膜厚は5μmであった。
導熱層形成用組成物として導熱層形成用組成物Y-7を使用した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ10秒および120秒であった。作製された導熱層の膜厚は5μmであった。
導熱層形成用組成物として導熱層形成用組成物Y-8を使用した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ10秒および120秒であった。作製された導熱層の膜厚は5μmであった。
導熱層形成用組成物として導熱層形成用組成物Y-9を使用し、かつ、最大回転速度を500rpmに変更した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ120秒および120秒であった。なお、回転速度を減少させるタイミングも、実施例1と同様に、固形分濃度が第1閾値濃度(濃度C=C1)に至った時刻に合わせた。作製された導熱層の膜厚は5μmであった。
スピンコータのノズルから導熱層形成用組成物を吐出させる際に、シリコンウェハの重心位置から5%外れた位置に向けて吐出した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ10秒および120秒であった。作製された導熱層の膜厚は5μmであった。
スピンコータのノズルから導熱層形成用組成物を吐出させる際に、シリコンウェハの重心位置から10%外れた位置に向けて吐出した点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ10秒および120秒であった。作製された導熱層の膜厚は5μmであった。
シリコンウェハを回転ステージに設置する際に、回転ステージの回転中心が、シリコンウェハの重心位置から水平方向に5%外れた位置にくるようにした点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ10秒および120秒であった。作製された導熱層の膜厚は5μmであった。
シリコンウェハを回転ステージに設置する際に、回転ステージの回転中心が、シリコンウェハの重心位置から水平方向に10%外れた位置にくるようにした点以外は、実施例1と同様の手順により、導熱層を作製した。第1の溶剤減量時間T1および第2の溶剤減量時間T3はそれぞれ10秒および120秒であった。作製された導熱層の膜厚は5μmであった。
スピンコータのノズルから導熱層形成用組成物を吐出させるタイミングを、回転ステージの回転開始前10秒時に設定した点以外は、実施例1と同様の手順により、導熱層を作製した。すなわち、実施例1の場合と同様に回転ステージ上に設置されたシリコンウェハの重心位置に向けて導熱層形成用組成物を吐出させて、導熱層形成用組成物をシリコンウェハ上に供給した。そして、導熱層形成用組成物を供給してから10秒後に、回転ステージの回転を開始し(時刻t=ta)、その回転速度を素早く300rpmに増加させた。さらに、回転速度が300rpmになってから5秒後に、回転ステージの回転速度を素早く1000rpmに増加させ、1000rpmの状態を維持した。このとき、第1の溶剤減量時間T1は20秒であった。その他の条件および手順は、実施例1の場合と同様である。なお、回転速度を減少させるタイミングも、実施例1と同様に、固形分濃度が第1閾値濃度(濃度C=C1)に至った時刻に合わせた。作製された導熱層の膜厚は5μmであった。
スピンコータの回転ステージの回転速度を常に900rpmで一定にした点以外は、実施例1と同様の手順により、導熱層を作製した。すなわち、実施例1の場合と同様にシリコンウェハが設置された回転ステージの回転を開始し(時刻t=ta)、その回転速度を900rpmに設定した。そして、回転速度が900rpmである状態で、シリコンウェハの重心位置に向けて導熱層形成用組成物を吐出させて、導熱層形成用組成物をシリコンウェハ上に供給した。このとき、第1の溶剤減量時間T1は10秒であった。その他の条件および手順は、実施例1の場合と同様である。なお、回転速度を減少させるタイミングも、実施例1と同様に、固形分濃度が第1閾値濃度(濃度C=C1)に至った時刻に合わせた。作製された導熱層の膜厚は5μmであった。
スピンコータの回転ステージの回転方向を反時計回り(左回り)にした点以外は、実施例1と同様の手順により、導熱層を作製した。このとき、第1の溶剤減量時間T1は10秒であった。作製された導熱層の膜厚は5μmであった。
スピンコータの回転ステージの回転終了時における角度位置が回転開始時と異なる点以外は、実施例1と同様の手順により、導熱層を作製した。このとき、第1の溶剤減量時間T1は10秒であった。作製された導熱層の膜厚は5μmであった。
スピンコータの回転ステージの回転速度を常に1000rpmで一定にし、かつ、スピンコータのノズルから導熱層形成用組成物を吐出させる際に、シリコンウェハの重心位置から水平方向に12%外れた位置に向けて吐出した点以外は、実施例1と同様の手順により、導熱層を作製した。すなわち、実施例1の場合と同様にシリコンウェハが設置された回転ステージの回転を開始し(時刻t=ta)、その回転速度を1000rpmに設定した。そして、回転速度が1000rpmである状態で、シリコンウェハの重心位置から水平方向に12%外れた位置に向けて導熱層形成用組成物を吐出させて、導熱層形成用組成物をシリコンウェハ上に供給した。このとき、第1の溶剤減量時間T1は9秒であった。その他の条件および手順は、実施例1の場合と同様である。なお、回転速度を減少させるタイミングも、実施例1と同様に、固形分濃度が第1閾値濃度(濃度C=C1)に至った時刻に合わせた。作製された導熱層の膜厚は5μmであった。
<<<実施例17>>>
基板として直径の最大値が150mmで外縁に47.5mmの直線部を有するシリコンウェハを使用し、導熱層形成用組成物として導熱層形成用組成物Y-10を使用した。
基板として直径の最大値が150mmで外縁に47.5mmの直線部を有するシリコンウェハを使用し、導熱層形成用組成物として導熱層形成用組成物Y-10を使用した。以下、図4を参照しながら手順を説明する。
<<<実施例19>>>
基板として直径の最大値が150mmで外縁に47.5mmの直線部を有するシリコンウェハを使用し、導熱層形成用組成物として導熱層形成用組成物Y-10を使用した。本実施例のタイムチャートも概略的には実施例17と同様である。
基板として直径の最大値が150mmで外縁に47.5mmの直線部を有するシリコンウェハを使用し、導熱層形成用組成物として導熱層形成用組成物Y-10を使用した。以下、図5を参照しながら手順を説明する。なお、図5中の符号のうち、図2中の符号と共通するものは、図2中の符号の意味と同義であり、図3中の符号と共通するものは、図3中の符号の意味と同義である。
上記で形成した各導熱層を次の方法でパターニングした。まず、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、365nmの波長の光を250mJ/cm2にて、直径50μmと10μmの二つのホールパターンを有するマスクを介して照射し、上記導熱層に露光処理を実施した。その後、露光された導熱層が形成されているシリコンウェハをスピンシャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、23℃で65秒間パドル現像を行い、各シリコンウェハ上に、2つのホールパターンが形成された導熱層を形成した。
上記で得た導熱層の特性評価として、熱伝導性、電気絶縁性、面状、スループット、パターン形成性、ダイシング、および耐熱試験後のダイシェア強度の各項目について、下記の方法で評価した。
熱伝導性は熱拡散率に基づいて評価した。熱拡散率は、周期加熱法(プラスチックの国際基準 ISO 22007-3準拠)に基づいて、熱拡散率測定装置FTC-RT(アドバンス理工製)で測定した。同じ厚さのシリコンウェハのリファレンスデータを取得して、その差分を算出することで測定した。熱拡散率は、ホールパターンを形成していない部分に装置を接触させて測定し、下記の4段階で評価した。
A:熱拡散率が1.0×10-6m2s-1以上である。
B:熱拡散率が5.0×10-7m2s-1以上1.0×10-6m2s-1未満である。
C:熱拡散率が3.0×10-7m2s-1以上5.0×10-7m2s-1未満である。
D:熱拡散率が3.0×10-7m2s-1未満である。
基板をシリコンウェハから、シリコンウェハ上に金をスパッタリングした基板に変更して、上記と同様にして、実施例1~29および比較例1に係る導熱層を形成した。電気絶縁性は、金電極上の導熱層体積抵抗率に基づいて評価した。体積抵抗率は、高抵抗用の抵抗率計として、ハイレスタ-UX MCP-HT800(JIS K6911に準拠)を使用して測定し、下記の4段階で評価した。
A:1.0×1012Ω・cm以上である。
B:1.0×1011Ω・cm以上1.0×1012Ω・cm未満である。
C:1.0×1010Ω・cm以上1.0×1011Ω・cm未満である。
D:1.0×1010Ω・cm未満である。
各実施例に係る乾燥後の導熱層に、紫外線フォトレジスト硬化装置(UMA-802-HC-552、ウシオ電機株式会社製)を用いて3000mJ/cm2の露光量にて紫外線を照射して硬化膜を形成した。次いで、中心を通るようにこの硬化膜を罫書き、接触式膜厚計(ブルカー社、Dektak XT)を用いて、膜厚の一番薄い部分(中心部)と一番厚い部分(周辺部)の膜厚を測定した。これらの測定値の差で面状を評価した。その差が小さいほど平坦性が高いといえる。
A:膜厚の差が0.1μm以下である。
B:膜厚の差が0.1μmより大きく0.25μm以下である。
C:膜厚の差が0.25μmより大きく0.5μm以下である。
D:膜厚の差が0.5μmより大きい。
支持体として「巴川製紙社製 熱伝導シートiCas KR」を円盤状にカットしたものを用い、後半の回転数(実施例1における1000rpm)を600rpmに変更した以外は実施例1と同様の手順により、導熱層を作製した。
導熱層形成用組成物としては、導熱層形成用組成物Y-1を使用した。
その後、実施例1と同様に、上記「<パターンの形成>」に記載の方法により導熱層のパターニング及び導熱層の硬化を行わなかった以外は、実施例1と同様の方法により、熱伝導性、電気絶縁性及び面状について評価した。評価結果はそれぞれ、下記表の「熱伝導性」、「絶縁性」、「面状」の欄に記載した。
また、後述の方法により「熱抵抗評価」および「ダイシェア強度評価」を行い、評価結果は下記表の「熱抵抗」および「ダイシェア強度」の欄にそれぞれ記載した。
支持体として下記方法により得られた支持体Aを用い、後半の回転数(実施例1における1000rpm)を600rpmに変更した以外は実施例1と同様の手順により、導熱層を作製した。
導熱層形成用組成物としては、導熱層形成用組成物Y-1を使用した。
その後、実施例1と同様に、上記「<パターンの形成>」に記載の方法により導熱層のパターニング及び導熱層の硬化を行わなかった以外は、実施例1と同様の方法により、熱伝導性、電気絶縁性及び面状について評価した。評価結果はそれぞれ、下記表の「熱伝導性」、「絶縁性」、「面状」の欄に記載した。
また、後述の方法により「熱抵抗評価」および「ダイシェア強度評価」を行い、評価結果は下記表の「熱抵抗」および「ダイシェア強度」の欄にそれぞれ記載した。
下記構造の化合物A-1とB-2を、当量(エポキシ化合物A-1のエポキシ基の数とフェノール化合物B-2の水酸基の数とが等しくなる量)で配合した混合物を調製した。
シクロペンタノンの添加量は組成物の固形分濃度が21.5質量%になる量とした。
トリフェニルホスフィンの添加量は、組成物中のトリフェニルホスフィンの含有量が、A-1の含有量に対して、1.7質量%となる量とした。
組成物中における上記混合物とトリフェニルホスフィンとの合計含有量は、組成物中における全固形分に対する合計含有量(質量%)が18.6質量%になる量とした。
組成物中における窒化ホウ素粒子の含有量は、組成物中における全固形分に対する合計含有量(体積%)が68.0体積%になる量(全固形分に対する合計含有量(質量%)が81.4質量%になる量)とした。
アプリケーターを用いて、離型処理したポリエステルフィルムの離型面上に、支持体形成用組成物を均一に塗布し、120℃で5分間放置して塗膜を得た。塗布量は、乾燥後の膜厚が290μmとなる量とした。
このようにして得られた塗膜付きフィルムの塗膜上に、更に、新たな上記ポリエステルフィルムを、離型面が対向するように張り合わせて、「ポリエステルフィルム-塗膜-ポリエステルフィルム」の構成を有する積層体を得た。
上記積層体にロールプレス処理をした。ロールプレス後の積層体を、空気下で熱プレス(熱板温度180℃、圧力20MPaで5分間処理した後、更に、常圧下で180℃90分間)で処理した。上記積層体の両面のポリエステルフィルムを剥がし、残った層を円盤状にカットすることによって支持体A(平均膜厚200μm)を得た。
各実施例と同様の方法により、それぞれ、アルミニウム製ウエハ上に導熱層(導熱層2)を形成した。
得られたアルミニウム製ウエハ上に形成された導熱層(導熱層2)に、各実施例において製造された導熱層(導熱層1)が形成された支持体の、導熱層とは接していない側の面を接触させた。
支持体上に形成した方の導熱層(導熱層1)の上面にヒーターおよび温度センサーを内蔵した3mm角のテストチップ(シーマ電子社製)を配置し、140℃、2分、接合時の圧力:0.5MPaの条件で、導熱層1を介してテストチップと支持体を、導熱層2を介して支持体とアルミニウム製ウエハを接合した。この接合は、チップボンダー(DB250、澁谷工業(株)製)を用いて行った。その後、175℃、2時間で加熱し、積層体を得た。
クーリングプレートを25℃に温度制御した状態で、ヒーターの出力が10Wになるように電源電圧、電流を調整し、チップ温度、周囲温度、消費電力を測定し、熱抵抗を算出した。評価基準は下記の通りとした。
A:熱抵抗が3.0K/W未満である。
B:熱抵抗が3.0K/W以上である。
熱抵抗測定を行なった後の積層体について、万能型ボンドテスター(DAGE4000 DAGE社製)を用いてダイシェアテストを行い、接着強度を測定した。評価基準は下記の通りとした。
A:接着強度が10MPa以上である。
B:接着強度が10MPa未満である。
表3~5に示すとおり、本発明の実施例1~28の導熱層の製造方法により、導熱層の熱伝導性および電気絶縁性が適切に発揮されることが分かった。
また、表6に示すとおり、実施例29~30の同熱層の製造方法により、導熱層の熱伝導性および電気絶縁性が適切に発揮されること、実施例29においてはダイシェア強度に優れること、実施例30においてはダイシェア強度及び熱抵抗に優れることが分かった。
2 樹脂膜
3 フィラー
4 導熱層
5 積層体
8 半導体モジュール
10 支持基板
11 リッド
12 第1の半導体チップ
13 第2の半導体チップ
15 冷却モジュール
20~23 接着層
25 中間層
32,33 LSIチップ
32a,33a 配線層
35a はんだバンプ
35b 樹脂絶縁層
35c 乾燥膜
36 はんだバンプ用のホール
E 熱エネルギー(放熱)
Claims (15)
- 樹脂、フィラーおよび溶剤を含みかつ固形分濃度が90質量%未満である導熱層形成用組成物を用いて、熱拡散率が3.0×10-7m2s-1以上である導熱層を支持体上に製造する製造方法であって、
前記導熱層形成用組成物を前記支持体に向けて吐出する吐出工程、および、
前記支持体上の位置ごとに、前記導熱層形成用組成物が吐出されてから前記導熱層形成用組成物中の固形分濃度が前記支持体上で90質量%に至るまでの第1の溶剤減量時間が10秒以上となるように、前記導熱層形成用組成物中の溶剤を減量する溶剤減量工程を含む、導熱層の製造方法。 - 前記第1の溶剤減量時間が、120秒以下である、
請求項1に記載の導熱層の製造方法。 - 前記溶剤減量工程において、前記導熱層形成用組成物中の固形分濃度が90質量%を超えた前記支持体上の位置に対し、雰囲気の減圧および前記支持体の加熱の少なくとも1種の溶剤減量処理を行う、
請求項1または2に記載の導熱層の製造方法。 - 前記支持体上の位置ごとに、前記導熱層形成用組成物中の固形分濃度が前記支持体上で90質量%を超えてから前記溶剤減量処理が開始されるまでの時間が、60秒以下である、
請求項3に記載の導熱層の製造方法。 - 前記支持体上の位置ごとに、前記導熱層形成用組成物中の固形分濃度が、前記支持体上で90質量%を超えてから、さらなる溶剤の減量により99質量%に至るまでの第2の溶剤減量時間が、60~300秒である、
請求項3または4に記載の導熱層の製造方法。 - 樹脂、フィラーおよび溶剤を含む導熱層形成用組成物を用いて、熱拡散率が3.0×10-7m2s-1以上である導熱層を支持体上に製造する製造方法であって、
スピンコート法により前記導熱層形成用組成物を前記支持体上に適用する適用工程を含み、
前記適用工程において前記導熱層形成用組成物を前記支持体上に供給する際に、前記支持体の適用面における重心を中心とし、かつ、前記重心と前記重心から最も離れた前記適用面上の点とをそれぞれ末端とする線分の長さの10%の長さを半径とする円領域に、前記導熱層形成用組成物を供給する、導熱層の製造方法。 - 前記導熱層形成用組成物が前記円領域に供給される前に前記支持体を回転させる、
請求項6に記載の導熱層の製造方法。 - 前記適用工程において、前記支持体の回転速度を変更する、
請求項6または7に記載の導熱層の製造方法。 - 前記適用工程において、前記支持体の回転方向が時計回りである、
請求項6~8のいずれか1項に記載の導熱層の製造方法。 - 前記適用工程において、前記支持体の回転終了時に、前記支持体の回転方向への角度位置を回転開始時と同じ角度位置に調整する、
請求項6~9のいずれか1項に記載の導熱層の製造方法。 - 前記支持体上に供給する前の前記導熱層形成用組成物の固形分濃度が90質量%未満であり、
前記適用工程が、前記導熱層形成用組成物を前記支持体に向けて吐出する吐出工程を含み、
前記支持体上の位置ごとに、前記導熱層形成用組成物が吐出されてから前記導熱層形成用組成物中の固形分濃度が前記支持体上で90質量%に至るまでの第1の溶剤減量時間が10秒以上となるように、前記支持体を回転させる、
請求項6~10のいずれか1項に記載の導熱層の製造方法。 - 前記フィラーの平均一次粒子径が10μm以下である、
請求項1~11のいずれか1項に記載の導熱層の製造方法。 - 前記フィラーの含有量が、前記導熱層形成用組成物中の全固形分量に対し50~75体積%である、
請求項1~12のいずれか1項に記載の導熱層の製造方法。 - 請求項1~13のいずれか1項に記載の導熱層の製造方法により、支持体上に前記導熱層を製造することを含む、前記支持体および前記導熱層を含む積層体の製造方法。
- 請求項1~13のいずれか1項に記載の導熱層の製造方法により、支持体上に前記導熱層を製造することを含む、前記支持体および前記導熱層を含む半導体デバイスの製造方法。
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JP7228707B2 (ja) | 2023-02-24 |
US11848249B2 (en) | 2023-12-19 |
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