TW201922905A - 具有改良之熱傳導性之介電層 - Google Patents
具有改良之熱傳導性之介電層 Download PDFInfo
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- TW201922905A TW201922905A TW107139143A TW107139143A TW201922905A TW 201922905 A TW201922905 A TW 201922905A TW 107139143 A TW107139143 A TW 107139143A TW 107139143 A TW107139143 A TW 107139143A TW 201922905 A TW201922905 A TW 201922905A
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Abstract
在一個實施例中,介電層包氟聚合物、複數個氮化硼顆粒、複數個二氧化鈦顆粒、複數個二氧化矽顆粒以及一加強層。介電層可包含20體積%至45體積%的氟聚合物、15體積%至35體積%的複數個氮化硼顆粒、1體積%至32體積%的複數個二氧化鈦顆粒、0體積%至35體積%的複數個二氧化矽顆粒以及5體積%至15體積%的加強層中之至少一者;其中體積百分比值係基於介電層之總體積。
Description
本申請案主張於2017年11月7日提出申請之美國臨時專利申請案第62/586,621號之權利。該相關申請案全文併入本案供參考。
本發明關於一種具有改良之熱傳導性之介電層。
電路子組件係用於製造單層電路及多層電路,且包括例如電路疊層、黏接片(bond ply)、樹脂塗覆的導電層及覆蓋膜,以及包裝基板疊層及構造材料。每一前述子組件皆含有一層介電材料。隨著電子器件及其上之特徵變得更小,所形成之密集電路佈局之熱管理變得愈來愈重要。已經進行了大量努力以藉由在介電層中引入導熱顆粒填料來改善電路疊層之熱傳導性。儘管已經顯示添加大量的導熱顆粒填料會增加熱傳導性,但是所增加量的導熱顆粒填料會不利地影響介電層之一或多種機械性質。
因此,此項技術中仍然需要改善電路疊層之熱傳導性而不會在其他性質中遭受不可接受的取捨。
本案揭露一種導熱介電層,該導熱介電層包氟聚合物及介電填料組成物。
在一個實施例中,介電層包含25體積%至45體積%的氟聚合物;15體積%至35體積%的複數個氮化硼顆粒;1體積%至32體積%的複數個二氧化鈦 顆粒;0體積%至35體積%的複數個二氧化矽顆粒;以及5體積%至15體積%的一加強層;其中體積百分比值係基於介電層之總體積。
本案亦揭露一種製造該介電層的方法,該方法包含:形成包含氟聚合物、複數個氮化硼顆粒、複數個二氧化鈦顆粒、複數個二氧化矽顆粒及複數個玻璃纖維的混合物;以及自該混合物形成該介電層;其中該介電層包含25體積%至45體積%的氟聚合物;15體積%至35體積%的複數個氮化硼顆粒;1體積%至32體積%的複數個二氧化鈦顆粒;0體積%至35體積%的複數個二氧化矽顆粒以及5體積%至15體積%的一加強層;其中體積百分比值係基於介電層之總體積。
另一種製造介電層的方法包含:用包含該氟聚合物、該複數個氮化硼顆粒、該複數個二氧化鈦顆粒及該複數個二氧化矽顆粒的混合物浸漬該加強層;其中該介電層包含25體積%至45體積%的氟聚合物;15體積%至35體積%的複數個氮化硼顆粒;1體積%至32體積%的複數個二氧化鈦顆粒;0體積%至35體積%的複數個二氧化矽顆粒;以及5體積%至15體積%的一加強層;其中體積百分比值係基於介電層之總體積。
本案更揭露一種物件,該物件包含該介電層;其中該介電層包含25體積%至45體積%的氟聚合物;15體積%至35體積%的複數個氮化硼顆粒;1體積%至32體積%的複數個二氧化鈦顆粒;0體積%至35體積%的複數個二氧化矽顆粒以及5體積%至15體積%的一加強層;其中體積百分比值係基於介電層之總體積。該物件可為包含該介電層的多層電路板。
上述及其他特徵係由以下附圖、實施方式及申請專利範圍加以例證。
12‧‧‧第一平面
14‧‧‧第二平面
16‧‧‧第一介電層部分
18‧‧‧第二介電層部分
20‧‧‧導電層
30‧‧‧導電層
32‧‧‧線內及平面內導電不連續部分
50‧‧‧單包層電路材料/雙包層電路材料
100‧‧‧介電層
300‧‧‧加強層
參考示例性非限制性附圖,其中在附圖中相像的元件標以相像的數字編號: 第1圖繪示介電層之橫剖面圖的一個實施例;第2圖繪示包含第1圖之介電層的單包層電路材料之橫剖面圖的一個實施例;第3圖繪示包含第1圖之介電層的雙包層電路材料之橫剖面圖的一個實施例;第4圖繪示具有圖案化貼片(patch)的金屬包層電路疊層之橫剖面圖的一個實施例。
氮化硼為高熱傳導陶瓷填料,通常用於電路材料之介電層中以增加其熱傳導性並有助於熱管理。雖然在介電層中摻入氮化硼會使得熱傳導性增加,但所增加量的氮化硼會導致機械性質降低。例如,端視填料之粒度分佈、表面積及表面化學性質而定,大於或等於50體積%之負載量可超過材料中粉末之最大充填率(packing ratio),使得添加額外的粉末會導致材料中所夾帶之空隙之數量增加,並且材料變脆。與介電層結合之銅箔之剝離強度為可受高負載量之氮化硼影響的機械性質的另一實例,乃因實現高熱傳導性所需之氮化硼之體積組成經常造成填充材料之表面偏析。此表面偏析會將銅箔剝離強度實質降低至低於工業規格的值。發現一種獨特的填料組成物能夠在保持高熱傳導性的同時允許氮化硼顆粒之量減少,該填料組成物包含複數個氮化硼顆粒;複數個二氧化鈦顆粒,該複數個二氧化鈦顆粒具有1微米至25微米的二氧化鈦D50值;以及複數個二氧化矽顆粒。例如,該填料組成物可包含15體積%至35體積%的複數個氮化硼顆粒;1體積%至32體積%的複數個二氧化鈦顆粒,該複數個二氧化鈦顆粒具有1微米至25微米的二氧化鈦D50值;以及0體積%至35體積%的複數個二氧化矽顆粒。如本文所用,藉由動態光散射來量測粒度。具體而言,該複數個二氧化鈦顆粒之獨特尺寸及量能夠減少氮化硼之量,從而改善介電層之熱性質。 該填料組成物實現此種高熱傳導性的能力令人驚訝,乃因原本預計用二氧化鈦代替一定量的氮化硼會導致熱傳導性降低。
更令人驚訝的是,在經加強介電層中觀察到此高熱傳導性,在經加強介電層中,加強層通常導致介電層之熱傳導性降低。具體而言,相對於實例1之介電層,根據ASTM D5470-12測定,本發明之介電層可實現大於或等於0.8的z方向相對z方向熱傳導性。在具有加強層之情形下實現高熱傳導性的能力改善了介電層之機械性質,實現了在沒有加強層之情形下無法達成的抗彎強度。
介電層包氟聚合物。如本文所用的「氟聚合物」包括均聚物及共聚物,該等均聚物及共聚物包含衍生自下列之重複單元:氟化α-烯烴單體,即包括至少一個氟原子取代基的α-烯烴單體的重複單元,以及視需要與該氟化α-烯烴單體反應的非氟化乙烯系不飽和單體。示例性氟化α-烯烴單體包括CF2=CF2、CHF=CF2、CH2=CF2、CHCl=CHF、CClF=CF2、CCl2=CF2、CClF=CClF、CHF=CCl2、CH2=CClF、CCl2=CClF、CF3CF=CF2、CF3CF=CHF、CF3CH=CF2、CF3CH=CH2、CHF2CH=CHF、CF3CF=CF2及全氟(C2-8烷基)乙烯醚,例如全氟甲基乙烯醚,全氟丙基乙烯醚及全氟辛基乙烯醚。氟化α-烯烴單體可包含四氟乙烯(CF2=CF2)、三氟氯乙烯(CClF=CF2)、(全氟丁基)乙烯、偏二氟乙烯(CH2=CF2)、六氟丙烯(CF2=CFCF3)、或包含前述中之至少一者的組合。示例性非氟化單乙烯系不飽和單體包括乙烯、丙烯、丁烯以及乙烯系不飽和芳族單體,例如苯乙烯及α-甲基-苯乙烯。示例性氟聚合物包括聚(三氟氯乙烯)(PCTFE)、聚(三氟氯乙烯-丙烯)、聚(乙烯-四氟乙烯)(ETFE)、聚(乙烯-三氟氯乙烯)(ECTFE)、聚(六氟丙烯)、聚(四氟乙烯)(PTFE)、聚(四氟乙烯-乙烯-丙烯)、聚(四氟乙烯-六氟丙烯)(亦稱為氟化乙烯-丙烯共聚物(FEP))、聚(四氟乙烯-丙烯)(亦稱為氟彈性體(FEPM))、聚(四氟乙烯-全氟丙烯)乙烯醚)、具有四氟乙烯主鏈及全氟化烷氧基側鏈的共聚物 (亦稱為全氟烷氧基聚合物(PFA))(例如,聚(四氟乙烯-全氟丙烯乙烯醚))、聚氟乙烯(PVF)、聚偏二氟乙烯(PVDF)、聚(偏二氟乙烯-三氟氯乙烯)、全氟聚醚、全氟磺酸及全氟聚氧雜環丁烷、或包含前述中之至少一者的組合。氟聚合物可包含全氟烷氧基烷烴聚合物或氟化乙烯-丙烯中之至少一者。氟聚合物可包含全氟烷氧基烷烴聚合物。可使用包含前述氟聚合物中之至少一者的組合。
在一些實施例中,氟聚合物為FEP、PFA、ETFE或PTFE中之至少一者,其可為原纖維形成的或非原纖維形成的。FEP可自杜邦公司(DuPont)以商品名TEFLON FEP或自大金公司(Daikin)以商品名NEOFLON FEP獲得;且PFA可自大金公司以商品名NEOFLON PFA、自杜邦公司以商品名TEFLON PFA或自蘇威蘇萊克斯公司(Solvay Solexis)以商品名HYFLON PFA獲得。
氟聚合物可包含PTFE。PTFE可包含PTFE均聚物、痕量改質的PTFE均聚物、或包含前述中之一者或二者的組合。如本文所用,基於聚合物之總重量,痕量改質的PTFE均聚物包含小於1重量%的衍生自除四氟乙烯以外的共聚單體的重複單元。
藉由將可交聯單體包含在氟聚合物之主鏈(包括氟聚合物之末端)中可使得氟聚合物可交聯。可交聯單體可藉由熟習此項技術者習知的任何熱交聯技術、化學交聯技術或光引發的交聯技術交聯,此端視所需的所得性質而定。示例性可交聯氟聚合物為包含(甲基)丙烯酸酯官能度(包括丙烯酸酯及甲基丙烯酸酯二者)的(甲基)丙烯酸酯氟聚合物。例如,可交聯氟聚合物可具有下式:H2C=CR′COO-(CH2)n-R-(CH2)n-OOCR′=CH2
其中R為如上所述之氟化α-烯烴單體或非氟化單乙烯系不飽和單體之寡聚物,R'為H或-CH3,且n為1至4。R可為包含衍生自四氟乙烯的單元的寡聚物。
交聯氟聚合物網路(network)可藉由將(甲基)丙烯酸酯氟聚合物暴露於自由基源以藉由氟聚合物上之丙烯酸酯基引發自由基交聯反應來製備。自由基源可為紫外(UV)光敏自由基起始劑或有機過氧化物之熱分解。合適的光起始劑以及有機過氧化物在此項技術中眾所習知。可交聯的氟聚合物可商購獲得,例如來自杜邦公司的VITON B。
基於介電層之總體積,介電層可包含20體積%至45體積%、或35體積%至45體積%的氟聚合物。
介電層包含填料組成物,填料組成物包含氮化硼、二氧化鈦及二氧化矽。填料組成物可包含氮化硼、金紅石二氧化鈦及二氧化矽。填料組成物可包含分別具有高介電常數及低介電常數的金紅石二氧化鈦及非晶形二氧化矽,乃因此組合可藉由調節它們各自的量而允許介電層中寬範圍的介電常數與低散逸因數組合。
介電層包含複數個氮化硼顆粒(在本文中亦稱為氮化硼)。氮化硼顆粒可為晶形的、多晶形的、非晶形的或其組合。氮化硼顆粒可為板晶形式(例如,六方板晶)。氮化硼顆粒可具有5微米至40微米、10微米至25微米、或12微米至20微米、或15微米至20微米的D50粒度。如本文所用,D50粒度對應於50%的顆粒數量大於D50值,且50%的顆粒數量小於D50值,如藉由雷射光散射所量測。當應用至氮化硼板晶時,D50值可指最大橫向尺寸。氮化硼板晶之厚度可為1微米至5微米、或1微米至2微米。橫向尺寸與厚度之比率可大於或等於5,或者大於或等於10。氮化硼顆粒之平均表面積可為0.5平方米/公克(m2/g)至20平方米/公克,或為1平方米/公克至15平方米/公克。
填料組成物可視需要更包含氮化硼纖維、氮化硼管、球形氮化硼顆粒、卵形氮化硼顆粒、不規則形狀的氮化硼顆粒、或包含前述中之至少一者的組合。氮化硼纖維及氮化硼管可具有10奈米至10微米的平均外徑以及大於或 等於1微米、或10微米至10公分(cm)、或500微米至1毫米的長度中的一者或二者。氮化硼纖維或氮化硼管可具有10至1,000,000、或20至500,000、或40至250,000的橫寬比(計算為長度/橫剖面尺寸)。
氮化硼可具有100瓦特/米.克耳文(W/m.K)至2,000瓦特/米.克耳文、或100瓦特/米.克耳文至1,800瓦特/米.克耳文、或100瓦特/米.克耳文至1,600瓦特/米.克耳文的熱傳導性。確定熱傳導性的方法係依據ASTM E1225-13。
基於介電層之總體積,介電層可包含15體積%至35體積%、或15體積%至30體積%、或18體積%至30體積%、或20體積%至25體積%的氮化硼顆粒。若介電層包含過少的氮化硼,則可能無法實現所需的熱傳導性,且若介電層包含過多的氮化硼,則可觀察到機械性質降低。
氮化硼顆粒可在介電層中形成黏聚物。黏聚物可具有1微米至200微米、或2微米至125微米、或3微米至40微米的平均黏聚物尺寸分佈(ASD)或直徑。氮化硼可作為黏聚物及/或非附聚的氮化硼顆粒之混合物存在。具體而言,根據介電層之透射電子顯微照片確定,50體積%或少於50體積%、30體積%或少於體積%、或10體積%或少於體積10%的氮化硼可在介電層中黏聚。
介電層包含複數個二氧化鈦顆粒(在本文中亦稱為二氧化鈦)。二氧化鈦可包含金紅石二氧化鈦、銳鈦礦二氧化鈦、或包含前述中之至少一者的組合。二氧化鈦可包含金紅石二氧化鈦。二氧化鈦顆粒之D50粒度可為1微米至40微米、或5微米至40微米、1微米至25微米、或1微米至20微米。二氧化鈦顆粒可為不規則的,具有複數個平坦表面。
基於介電層之總體積,介電層可包含0體積%至40體積%、1體積%至35體積%、或1體積%至32體積%、或1體積%至10體積%的二氧化鈦顆粒。
介電層可包含複數個二氧化矽顆粒(在本文中亦稱為二氧化 矽)。二氧化矽顆粒可包含微晶二氧化矽、非晶形二氧化矽(例如,熔融非晶形二氧化矽)、或包含前述中之至少一者的組合。二氧化矽顆粒可為球形或不規則的。二氧化矽顆粒之D50粒度可為5微米至15微米、或5微米至10微米。即使納入加強層,二氧化矽顆粒之小粒度亦可產生良好的介電性質。
基於介電層之總體積,介電層可包含0體積%至35體積%、或0體積%至25體積%、或15體積%至30體積%的二氧化矽顆粒。
填料組成物可更包含鈦酸鈣、鈦酸鋇、鈦酸鍶、玻璃珠、或包含前述中之至少一者的組合。填料組成物可更包含SrTiO3、CaTiO3、BaTiO4、Ba2Ti9O20、或包含前述中之至少一者的組合。
氮化硼與二氧化矽之體積比可為1:0至1:2、或1:0至1:1.5、或1:0.5至1:1.5、或1:0.8至1:1.4。氮化硼之D50值與二氧化矽之D50值之比可為1:0.25至1:1.25、或1:0.3至1:1.1、或1:0.25至1:0.75、或1:0.4至1:0.6。氮化硼與二氧化鈦之體積比可為1:0.01至1:1.7、或1:0.2至1:1.5。氮化硼與二氧化鈦之體積比可為1:0.1至1:0.6、或1:0.2至1:0.4。氮化硼之D50值與二氧化鈦之D50值之比可為1:0.1至1:2.5、或1:0.1至1:2。氮化硼之D50值與二氧化鈦之D50值之比可為1:0.8至1:1.2。
可對氮化硼顆粒、二氧化鈦顆粒及二氧化矽顆粒中之一或多者進行表面處理以幫助分散到氟聚合物中,例如,用表面活性劑、矽烷、有機聚合物或其他無機材料進行表面處理。例如,顆粒可塗覆有表面活性劑,例如油胺油酸等。矽烷可包含N-β(胺基乙基)-γ-胺基丙基三乙氧基矽烷、N-β(胺基乙基)-γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、3-氯丙基-甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、苯基矽烷、 三氯(苯基)矽烷、3-(三乙氧基矽基)丙基琥珀酸酐、三(三甲基矽氧基)苯基矽烷、乙烯基苄基胺基乙基胺基丙基三甲氧基矽烷、乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三(β甲氧基乙氧基)矽烷、或包含前述中之至少一者的組合。矽烷可包含苯基矽烷。矽烷可包含經取代的苯基矽烷,例如美國專利4,756,971中所述的彼等。基於塗覆顆粒之總重量,矽烷可係以0.01重量%至2重量%、或0.1重量%至1重量%存在。顆粒可塗覆有SiO2、Al2O3、MgO、銀或包含前述中之一或多者的組合。可藉由鹼催化的溶膠-凝膠技術、聚醚醯亞胺(PEI)濕式及乾式塗佈技術、或聚(醚醚酮)(PEEK)濕式及乾式塗佈技術塗佈顆粒。
氮化硼顆粒可包含表面塗層,該表面塗層包含陶瓷、金屬氧化物、金屬氫氧化物、或包含前述中之至少一者的組合。表面塗層可包含二氧化矽、氧化鋁、水鋁石、氫氧化鎂、二氧化鈦、碳化矽、碳氧化矽、或包含前述中之至少一者的組合。表面塗層可係衍生自聚矽氮烷、聚碳矽烷、矽氧烷、聚矽氧烷、聚碳矽氧烷、倍半矽氧烷、聚倍半矽氧烷、聚碳矽氮烷、或包含前述中之至少一者的組合。
介電層包含一加強層,該加強層包含複數個纖維,該複數個纖維可在固化期間幫助控制介電層平面內之收縮,且相對於沒有加強層的相同介電層可提供增加的機械強度。加強層可為紡織層或非紡織層。纖維可包含玻璃纖維(例如E玻璃纖維、S玻璃纖維及D玻璃纖維)、二氧化矽纖維、聚合物纖維(例如聚醚醯亞胺纖維、聚碸纖維、聚(醚酮)纖維、聚酯纖維、聚醚碸纖維、聚碳酸酯纖維、芳族聚醯胺纖維、液晶聚合物纖維如可自可樂麗公司(Kuraray)購得的VECTRAN)、或包含前述中之至少一者的組合。纖維之直徑可為10奈米至10微米。加強層可具有小於或等於200微米、或50微米至150微米的厚度。介電層可包含5體積%至15體積%、或6體積%至10體積%、或7體積%至11體積%、 或7體積%至9體積%的加強層。
介電層之厚度將端視其預期用途而定。介電層之厚度可為5微米至1,000微米、或5微米至500微米、或5微米至400微米。在另一個實施例中,當用作介電基板層時,複合物之厚度為250微米至4,000微米、或500微米至2,000微米、或500微米至1,000微米。
在10吉赫(GHz)之頻率下量測,介電層可具有大於或等於2、或2至6.5、或2至5的介電係數。在10吉赫之頻率下量測,介電層可具有小於或等於0.003的耗散因數。介電係數(Dk)及介電損耗或耗散因數(Df)可根據「X波段的介電係數及損耗角正切帶線試驗(Stripline Test for Permittivity and Loss Tangent at X-Band)」試驗方法IPC-TM-6502.5.5.5在23℃至25℃的溫度下量測。
介電層可具有0.5瓦特/米.克耳文至10瓦特/米.克耳文、或0.5瓦特/米.克耳文至5瓦特/米.克耳文、或1瓦特/米.克耳文至2瓦特/米.克耳文的z方向熱傳導性。「方向熱傳導性」指在垂直於介電層平面之方向上之熱傳導性。z方向熱傳導性可根據ASTM D5470-12量測。
可藉由用包含氟聚合物、複數個氮化硼顆粒、複數個二氧化鈦顆粒、可選的複數個二氧化矽顆粒及可選的溶劑的混合物浸漬加強層來製備介電層。浸漬可包含將混合物澆鑄到加強層上或將加強層浸塗到混合物中,或將混合物輥塗到加強層上。
可如下製備介電層:在水中形成包含填料組成物及複數個玻璃纖維的混合物;將氟聚合物以分散體的形式加入例如水中;以及成形介電層。成形可包含糊料擠出及壓延。成形可包含在造紙機上成形。
可藉由混合氟聚合物、複數個氮化硼顆粒、複數個二氧化鈦顆粒、複數個二氧化矽顆粒及可選的溶劑來形成混合物。可藉由混合包含複數個氮化硼顆粒、複數個二氧化鈦顆粒、複數個二氧化矽顆粒及可選的填料組成物 溶劑的填料組成物與包含氟聚合物及可選的氟聚合物組成物溶劑的氟聚合物組成物混合來形成混合物。可藉由將混合物計量到正確的厚度來控制介電層之厚度。在形成加強層之後,可除去任何溶劑。
可存在溶劑以調節混合物之黏度且可有助於形成介電層,例如,在加強層之浸漬期間。可選擇溶劑以溶解或分散氟聚合物及填料組成物,並具有方便的蒸發速率以施加混合物並乾燥介電層。溶劑及分散介質之非排他性列表包括醇(如甲醇、乙醇及丙醇)、環己烷、庚烷、己烷、異佛爾酮、甲基乙基酮、甲基異丁基酮、壬烷、辛烷、甲苯、水、二甲苯、及萜烯類溶劑。例如,溶劑可包含己烷、甲基乙基酮、甲基異丁基酮、甲苯、二甲苯、或包含前述中之至少一者的組合。溶劑可包含水。當形成介電基板的方法包含形成填料組成物及氟聚合物組成物時,填料組成物溶劑及氟聚合物組成物溶劑可相同或不同。例如,氟聚合物組成物溶劑可包含水且填料組成物溶劑可包含醇。
該混合物可包含黏度調節劑以例如藉由沉降或浮選來延遲填料組成物與氟聚合物之分離,並使混合物具有與形成介電層相匹配的黏度。示例性黏度調節劑包括聚丙烯酸、植物膠及基於纖維素的化合物。黏度調節劑之具體實例包括聚丙烯酸、甲基纖維素、聚環氧乙烷、瓜爾膠、刺槐豆膠、羧甲基纖維素鈉、海藻酸鈉及黃蓍膠。或者,若溶劑之黏度足以提供在相關時間段內不分離的混合物,則可省略黏度調節劑。
在浸漬加強層之後,可加熱介電層,例如,以除去任何溶劑或黏度調節劑,或燒結氟聚合物。
可如下形成疊層:形成包含一或多個介電層及一或多個導電層的多層疊層;以及層壓該多層疊層。黏合層可視需要存在於多層疊層中以促進其間之黏合。多層疊層可在壓力及溫度下放置在壓機中,例如真空壓機中,持續一段適於黏接各層並形成疊層的時間。或者,介電基板可沒有導電層,例如銅 箔。
可藉由形成具有介電層及設置於介電層之上之導電層的多層材料來製備包含介電層的電路材料。有用的導電層包括例如不銹鋼、銅、金、銀、鋁、鋅、錫、鉛、過渡金屬或包含前述中之至少一者的合金。關於導電層之厚度並無特別限制,導電層表面之形狀、尺寸或紋理亦無任何限制。導電層可具有3微米至200微米、或9微米至180微米的厚度。當存在兩個或更多個導電層時,兩個層之厚度可相同或不同。導電層可包含銅層。合適的導電層包括由導電金屬形成之薄層,例如目前用於形成電路的銅箔,例如電沉積銅箔。銅箔之均方根(RMS)粗糙度可小於或等於2微米、或小於或等於0.7微米,其中粗糙度使用觸針式輪廓儀量測。
可藉由層壓導電層及介電層、藉由直接雷射成型、或藉由經由黏合層將導電層黏附到基板來施加導電層。可使用此項技術中習知的其他方法在特定材料及電路材料之形式允許的情形下施加導電層,例如電沉積、化學氣相沉積等。
層壓可能需要層壓多層疊層,該多層疊層包含介電層、導電層及位於介電層與導電層之間的可選中間層,以形成分層結構。導電層可與介電層直接接觸,而沒有中間層。然後可在壓力及溫度下將分層結構置於壓機(例如真空壓機)中一段適合於黏合各層並形成層壓材料的時間。層壓及可選的固化可藉由例如使用真空壓機的一步法進行,或者可藉由多步法進行。在一步法中,可將分層結構置於壓機中,使其達到層壓壓力(例如,150磅/平方英吋(psi)至1,200磅/平方英吋)(1.0百萬帕斯卡至8.3百萬帕斯卡)並加熱至層壓溫度(例如,260攝氏度(℃)至390℃)。層壓溫度及壓力可保持所需的持溫時間,例如20分鐘,然後冷卻(同時仍處於壓力下)至小於或等於150℃。
若存在,中間層可包含可位於導電層與介電層之間的多氟碳膜, 且由微玻璃增強碳氟聚合物形成的可選層可位於多氟碳膜與導電層之間。微玻璃增強碳氟聚合物層可增加導電層與基板之黏著。基於層之總重量,微玻璃可係以4重量%至30重量%的量存在。微玻璃可具有小於或等於900微米、或小於或等於500微米的最長長度尺度。微玻璃可為科羅拉多州丹佛市的約翰斯-曼維爾公司(Johns-Manville Corporation of Denver,Colorado)市售類型的微玻璃。多氟烴膜包含氟聚合物(例如聚四氟乙烯、氟化乙烯-丙烯共聚物及具有四氟乙烯主鏈及完全氟化的烷氧基側鏈的共聚物)。
可藉由雷射直接成型來施加導電層。此處,介電層可包含雷射直接成型添加劑;且雷射直接成型可包含使用雷射照射基板表面,形成雷射直接成型添加劑之軌道(track),以及將導電金屬施加到軌道上。雷射直接成型添加劑可包含金屬氧化物顆粒(例如氧化鈦及氧化銅鉻)。雷射直接成型添加劑可包含尖晶石基無機金屬氧化物顆粒,例如尖晶石銅。金屬氧化物顆粒可例如用包含錫及銻的組成物(例如,基於塗層之總重量,50重量%至99重量%的錫及1重量%至50重量%的銻)塗覆。基於100份相應的組成物,雷射直接成型添加劑可包含2份至20份添加劑。照射可用波長為1,064奈米的YAG雷射在10瓦特的輸出功率、80千赫(kHz)的頻率及3米/秒的速率下進行。可在包含例如銅的無電鍍浴中使用電鍍法施加導電金屬。
可藉由以黏合方式施加導電層來施加導電層。導電層可為電路(另一電路之金屬化層),例如撓性電路。黏合層可設置在一個或多個導電層與基板之間。
第1圖中示出了示例性介電層。介電層100包含氟聚合物、填料組成物及加強層300。加強層300可為紡織層或非紡織層。介電層100具有第一平面12及第二平面14。介電層100可具有位於加強層一側的第一介電層部分16以及位於加強層第二側的第二介電層部分18。如本文所用,術語「第一介電」及「第 二介電」指加強層300每一側上之區域,且不將各種實施例限制至兩個分開的部分。
雖然第1圖及第2圖中藉由具有「線厚度」的波浪線描繪示了加強層300,但可理解,此種繪示是出於一般說明性目的,並非旨在限制本文所揭露實施例之範圍。加強層300可為紡織或非紡織纖維材料,允許介電層100之間經由加強層300中之空隙接觸。
包含第1圖之介電層100的示例性電路材料示於第2圖中,其中導電層20設置於介電層100之平坦表面14上以形成單包層電路材料50。如此處及整個本揭露中所使用,「設置」意指該等層部分或全部彼此覆蓋。中介層(例如,黏合層)可存在於導電層20與介電層100之間(未示出)。
第3圖中示出了另一示例性實施例,其中雙包層電路材料50包含第1圖之介電層100,介電層100設置在兩個導電層20及30之間。導電層20及30中的一者或二者可呈電路的形式(未示出),以形成雙包層電路。可在介電層100之一側或兩側上使用黏合劑(未示出)以增加介電層與導電層之間的黏合。可添加另外的層以產生多層電路。
第4圖繪示了雙包層電路材料50,其導電層30藉由蝕刻、銑削或任何其他合適方法加以圖案化。如本文所用,術語「圖案化」包括導電元件30具有線內(in-line)及平面內導電不連續部分32的佈置。電路材料還可包括訊號線,訊號線可為同軸電纜、饋電帶或微帶之中心訊號導體,例如,可設置成與導電元件30訊號通訊。所提供之同軸電纜可具有圍繞中心訊號線設置的接地護套,接地護套可設置成與導電接地層20進行電對地通訊。
介電層可用於各種電路材料中。如本文所用,電路材料為用於製造電路及多層電路的物件,且包括例如電路子組件、黏接片、樹脂塗覆的導電層、未包層介電層、自由膜及覆蓋膜。電路子組件包括具有固定地連接到介電 層的導電層(例如銅)的電路疊層。雙包層電路疊層具有兩個導電層,在介電層之每一側上各有一個導電層。例如藉由蝕刻圖案化疊層之導電層提供電路。多層電路包含複數個導電層,其中至少一個導電層可含有導電佈線圖案。通常,藉由使用黏接片將一或多個電路層壓在一起、藉由用隨後被蝕刻的樹脂塗覆的導電層構建附加層、或者藉由添加未包層介電層然後進行附加金屬化來構建附加層而形成多層電路。在形成多層電路之後,可使用習知的孔形成及電鍍技術在導電層之間產生有用的電通路。
介電層可用於天線中。天線可用於移動電話(例如智能電話)、平板電腦、筆記本電腦等中。
提供以下實例以說明本揭露。該等實例僅僅是說明性的,並非旨在將根據本揭露所製造之器件限制至本文中所述的材料、條件或製程參數。
實例
表1中列出之所用材料用於以下實例中。
在各實例中,相對熱傳導性係基於根據ASTM D5470-12測定的z方向熱傳導性。
例1-11
藉由用聚四氟乙烯及表2中所定義之填料組成物浸漬紡織玻璃纖維加強層來製備介電層,其中所有量皆以體積百分比顯示,且相對TC指相對於實例1的z方向熱傳導性。
表2顯示,將二氧化鈦之粒度自實例1之16微米之D50值改變為實例2之3微米之D50值仍然提供80%的相對z方向熱傳導性。
表2亦顯示,將二氧化矽顆粒形態自實例1之球形改變為實例3之非球形,同時維持顆粒尺寸,不會強烈影響熱傳導性。
在實例4中,玻璃纖維加強物之體積百分比增加至16.2體積%。儘管陶瓷組分具有與實例1相同的尺寸及形態,但加強物體積增加使相對熱傳導性降低至低於實例1中之相對熱傳導性之75%。
在實例5中,玻璃纖維加強物之體積百分比降低至8.0體積%。玻璃纖維加強材料之體積百分比的此微小變化不會強烈影響z方向熱傳導性。
在實例6中,對二氧化鈦及二氧化矽之比率進行了微小的改變。該些小變化能夠調節介電係數,但不會強烈影響熱傳導性。
在實例7中,用氧化鋁代替二氧化鈦。材料中之此種變化使相對熱傳導性降低到低於實施例1中之熱傳導性之75%。
在實例8及實例10中,改變氮化硼之尺寸,同時維持顆粒幾何形狀。此種變化未對熱傳導性產生很大影響。
在比較實例8與實例9時,改變二氧化鈦之尺寸,同時保持顆粒幾何形狀。此種變化未對熱傳導性產生很大影響。
在實例11中,二氧化鈦之量減少至僅1.0體積%。雖然觀察到相對z方向熱傳導性出現降低,但仍在實例1中所示值之80%以內。
以下闡述的是本揭露之各種非限制性實施方案。
實施方案1:一種介電層,包含:氟聚合物、複數個氮化硼顆粒、複數個二氧化鈦顆粒、複數個二氧化矽顆粒以及一加強層。該介電層可包含20體積%至45體積%的該氟聚合物、15體積%至35體積%的該複數個氮化硼顆粒、1體積%至32體積%的該複數個二氧化鈦顆粒、0體積%至35體積%的該複數個二氧化矽顆粒以及5體積%至15體積%的該加強層中之至少一者;其中該等體積百分比值係基於該介電層之總體積。
實施方案2:如實施方案1所述之介電層,其中該氟聚合物包含聚(三氟氯乙烯)、聚(三氟氯乙烯-丙烯)、聚(乙烯-四氟乙烯)、聚(乙烯-三氟氯乙烯)、聚(六氟丙烯)、聚(四氟乙烯)、聚(四氟乙烯-乙烯-丙烯)、聚(四氟乙烯-六氟丙烯)、聚(四氟乙烯-丙烯)、聚(四氟乙烯-全氟丙烯乙烯醚)、具有四氟乙烯主鏈及全氟化烷氧基側鏈的共聚物、聚氟乙烯、聚偏二氟乙烯、聚(偏二氟乙烯-三氟氯乙烯)、全氟聚醚、全氟磺酸、全氟聚氧雜環丁烷、或包含前述中之至少一者的組合。
實施方案3:如前述實施方案中任一或更多實施方案所述之介電層,其中該氟聚合物包含聚四氟乙烯。
實施方案4:如前述實施方案中任一或更多實施方案所述之介電層,其中該介電層包含18體積%至30體積%的該複數個氮化硼顆粒。
實施方案5:如前述實施方案中任一或更多實施方案所述之介電層,其中該複數個氮化硼顆粒包含氮化硼板晶(platelet),較佳為六方氮化硼板晶。
實施方案6:如前述實施方案中任一或更多實施方案所述之介電層,其中該複數個氮化硼顆粒具有5微米至40微米的氮化硼D50值。
實施方案7:如前述實施方案中任一或更多實施方案所述之介電層,其中該介電層包含1體積%至10體積%的該複數個二氧化鈦顆粒。
實施方案8:如前述實施方案中任一或更多實施方案所述之介電層,其中該二氧化鈦包含金紅石二氧化鈦。
實施方案9:如前述實施方案中任一或更多實施方案所述之介電層,其中該複數個二氧化鈦顆粒包含不規則形狀的顆粒,每一顆粒獨立地具有複數個平坦表面。
實施方案10:如前述實施方案中任一或更多實施方案所述之介電層,其中該二氧化鈦D50值為1微米至40微米,或者為1微米至25微米。
實施方案11:如前述實施方案中任一或更多實施方案所述之介電層,其中該介電層包含15體積%至25體積%的該複數個二氧化矽顆粒。
實施方案12:如前述實施方案中任一或更多實施方案所述之介電層,其中該複數個二氧化矽顆粒具有5微米至15微米的二氧化矽D50值。
實施方案13:如前述實施方案中任一或更多實施方案所述之介電層,其中該二氧化矽包含非晶形二氧化矽。
實施方案14:如前述實施方案中任一或更多實施方案所述之介電層,,其中該複數個氮化硼顆粒、該複數個二氧化鈦顆粒及該複數個二氧化矽 顆粒中的一或多者包含表面處理。
實施方案15:如前述實施方案中任一或更多實施方案所述之介電層,其中該加強層包含紡織玻璃纖維加強物或非紡織玻璃纖維加強物。
實施方案16:如前述實施方案中任一或更多實施方案所述之介電層,該介電層具有1瓦特/米.克耳文(W/m.K)至2瓦特/米.克耳文的z方向熱傳導性。
實施方案17:一種製造介電層的方法,例如製造如前述實施方案中任一實施方案所述之介電層,該方法包含:用包含氟聚合物、複數個氮化硼顆粒、複數個二氧化鈦顆粒及複數個二氧化矽顆粒的混合物浸漬加強層,以形成該介電層。
實施方案18:如實施方案17所述之方法,其中浸漬包含浸塗或澆鑄。
實施方案19:一種製造介電層的方法,例如製造如實施方案1至16中任一實施方案所述之介電層,該方法包含:形成包含氟聚合物、複數個氮化硼顆粒、複數個二氧化鈦顆粒、複數個二氧化矽顆粒及複數個玻璃纖維的混合物;以及自該混合物形成該介電層。
實施方案20:如實施方案19所述之方法,其中形成該介電層包含糊料擠出及壓延。
實施方案21:一種物件,包含如前述實施方案中任一實施方案所述之介電層。
實施方案22:一種多層電路板,包含如前述實施方案中任一實施方案所述之介電層。
實施方案23:如實施方案22所述之多層電路板,其中該介電層具有1瓦特/米.克耳文至2瓦特/米.克耳文的z方向熱傳導性。
或者,該等組成物、方法及物件可包含本文所揭露之任何適當的材料、步驟或組分,由本文所揭露之任何適當的材料、步驟或組分組成,或基本上由本文所揭露之任何適當的材料、步驟或組分組成。該等組成物、方法及物件可另外地或替代地配製成不含或實質上不含對於實現該等組成物、方法及物件之功能或目的而言原本不是必需的任何材料(或物質)、步驟或組分。
術語「一(a及an)」不表示數量限制,而是表示存在至少一個所引用項。除非上下文另有明確說明,否則術語「或」表示「及/或」。整個說明書中對「一個實施方案」,「一個實施例」、「另一個實施例」、「一些實施例」等的引用意指結合該實施例所闡述之特定元件(例如,特徵、結構、步驟或特性)被包含在本文所述的至少一個實施例中,並且可存在或不存在於其他實施例中。另外,應理解,所闡述之元件可在各種實施例中以任何合適的方式組合。「可選的」或「視需要」表示隨後描述的事件或情形可能發生或可能不發生,並且該闡述包括事件發生的情形和事件不發生的情形。術語「組合」包括摻混物、混合物、合金、反應產物等。此外,「包含前述至少一者的組合」意指列表單獨包括每一元件,以及列表中之而或更多個元件之組合,以及列表中之至少一個元件與相似的未命名元件之組合。
除非本文另有說明,否則所有試驗標準皆為本申請案提交日期(或者,若主張優先權,則為出現試驗標準的最早優先權申請案之提交日期)時有效的最新標準。
針對相同組分或性質的所有範圍之端點包括端點,可獨立地組合,並包括所有中間點及範圍。例如,「至多25體積%、或5體積%至20體積%」之範圍包括端點及「5體積%至25體積%」範圍中之所有中間值,例如10體積%至23體積%等。
除非另外定義,否則本文使用之科技術語具有與熟習本揭露所屬技術者通常理解之含義相同的含義。
所有引用的專利、專利申請及其他參考文獻皆全文併入本案供參考。然而,若本申請案中之術語與所併入之參考文獻中之術語相矛盾或衝突,則來自本申請案之術語優先於來自所併入之參考文獻之衝突術語。
雖然已經闡述了特定實施例,但申請人或其他熟習此項技術者可想到當前無法預見或可能無法預見的替代、修改、變化、改進及實質等同物。因此,所提交的以及可能加以修改的隨附請求項旨在涵蓋所有該些替代、修改、變化、改進及實質等同物。
Claims (22)
- 一種介電層,包含:25體積%至45體積%的氟聚合物;15體積%至35體積%的複數個氮化硼顆粒;1體積%至32體積%的複數個二氧化鈦顆粒;0體積%至35體積%的複數個二氧化矽顆粒;以及5體積%至15體積%的一加強層;其中該等體積百分比值係基於該介電層之總體積。
- 如請求項1所述之介電層,其中該氟聚合物包含聚(三氟氯乙烯)、聚(三氟氯乙烯-丙烯)、聚(乙烯-四氟乙烯)、聚(乙烯-三氟氯乙烯)、聚(六氟丙烯)、聚(四氟乙烯)、聚(四氟乙烯-乙烯-丙烯)、聚(四氟乙烯-六氟丙烯)、聚(四氟乙烯-丙烯)、聚(四氟乙烯-全氟丙烯乙烯醚)、具有四氟乙烯主鏈及全氟化烷氧基側鏈的共聚物、聚氟乙烯、聚偏二氟乙烯、聚(偏二氟乙烯-三氟氯乙烯)、全氟聚醚、全氟磺酸、全氟聚氧雜環丁烷、或包含前述中之至少一者的組合。
- 如請求項1所述之介電層,其中該氟聚合物包含聚四氟乙烯。
- 如請求項1所述之介電層,其中該介電層包含15體積%至30體積%的該複數個氮化硼顆粒。
- 如請求項1所述之介電層,其中該複數個氮化硼顆粒包含氮化硼板晶(platelet)。
- 如請求項1所述之介電層,其中該複數個氮化硼顆粒具有5微米至40微米的氮化硼D 50值。
- 如請求項1所述之介電層,其中該介電層包含5體積%至10體積%的該複數個二氧化鈦顆粒。
- 如請求項1所述之介電層,其中該二氧化鈦包含金紅石二氧化鈦。
- 如請求項1所述之介電層,其中該複數個二氧化鈦顆粒包含不規則形狀的顆粒,每一顆粒獨立地具有複數個平坦表面。
- 如請求項1所述之介電層,其中該二氧化鈦D 50值為1微米至40微米。
- 如請求項1所述之介電層,其中該介電層包含15體積%至25體積%的該複數個二氧化矽顆粒。
- 如請求項1所述之介電層,其中該複數個二氧化矽顆粒具有5微米至15微米的二氧化矽D 50值。
- 如請求項1所述之介電層,其中該二氧化矽包含非晶形二氧化矽。
- 如請求項1所述之介電層,其中該複數個氮化硼顆粒、該複數個二氧化鈦顆粒及該複數個二氧化矽顆粒中的一或多者包含表面處理。
- 如請求項1所述之介電層,其中該加強層包含紡織玻璃纖維加強物或非紡織玻璃纖維加強物。
- 一種製造如請求項1所述之介電層的方法,包含:用包含該氟聚合物、該複數個氮化硼顆粒、該複數個二氧化鈦顆粒及該複數個二氧化矽顆粒的混合物浸漬該加強層,以形成該介電層。
- 如請求項16所述之方法,其中該浸漬包含浸塗或澆鑄。
- 一種製造如請求項1所述之介電層的方法,包含:形成包含該氟聚合物、該複數個氮化硼顆粒、該複數個二氧化鈦顆粒、該複數個二氧化矽顆粒及複數個玻璃纖維的混合物;以及自該混合物形成該介電層。
- 如請求項18所述之方法,其中該形成該介電層包含糊料擠出及壓延。
- 一種物件,包含如請求項1所述之介電層。
- 一種多層電路板,包含如請求項1所述之介電層。
- 如請求項21所述之多層電路板,其中該介電層具有1瓦特/米.克耳文(W/m.K)至2瓦特/米.克耳文的z方向熱傳導性。
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CN109912908B (zh) * | 2017-12-13 | 2021-05-18 | 财团法人工业技术研究院 | 基板组合物及由其所制备的基板 |
WO2019239320A1 (en) | 2018-06-12 | 2019-12-19 | 3M Innovative Properties Company | Fluoropolymer compositions comprising fluorinated additives, coated substrates and methods |
US12018144B2 (en) | 2018-06-12 | 2024-06-25 | 3M Innovative Properties Company | Fluoropolymer coating compositions comprising amine curing agents, coated substrates and related methods |
GB201810710D0 (en) * | 2018-06-29 | 2018-08-15 | Smartkem Ltd | Sputter Protective Layer For Organic Electronic Devices |
JPWO2020235532A1 (zh) * | 2019-05-21 | 2020-11-26 | ||
KR102676453B1 (ko) | 2019-07-16 | 2024-06-20 | 다이킨 고교 가부시키가이샤 | 회로 기판용 수지 조성물, 회로 기판용 성형체, 회로 기판용 적층체 및 회로 기판 |
CN110809357A (zh) * | 2019-10-21 | 2020-02-18 | 鹤山市世安电子科技有限公司 | 耐高温pcb板及其制造方法 |
US20210130573A1 (en) * | 2019-10-30 | 2021-05-06 | Hamilton Sundstrand Corporation | Polymer-ceramic composite and methods of making the same |
WO2021088198A1 (en) * | 2019-11-04 | 2021-05-14 | 3M Innovative Properties Company | Electronic telecommunications articles comprising crosslinked fluoropolymers and methods |
CN111642076A (zh) * | 2020-04-29 | 2020-09-08 | 信维通信(江苏)有限公司 | 一种二维材料填充覆铜板的制造工艺 |
TWI766320B (zh) * | 2020-07-23 | 2022-06-01 | 南亞塑膠工業股份有限公司 | 預浸片及金屬積層板 |
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TW202206286A (zh) | 2020-07-28 | 2022-02-16 | 美商聖高拜塑膠製品公司 | 介電基板及其形成方法 |
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WO2018093987A1 (en) * | 2016-11-16 | 2018-05-24 | Rogers Corporation | Method for the manufacture of thermally conductive composite materials and articles comprising the same |
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JP6691274B2 (ja) | 2020-04-28 |
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