TWI662561B - Lead-free thick film resistor composition, lead-free thick film resistor and production method thereof - Google Patents
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Abstract
本發明係關於一種無鉛厚膜電阻組合物、一種無鉛厚膜電阻及其製造方法。更具體地,本發明係關於一種無鉛厚膜電阻組合物、無鉛厚膜電阻、及其製造方法,該無鉛厚膜電阻組合物包括含有釕系複合氧化物及玻璃成分以形成雙重網絡結構之導電複合粉末,使得即使不含鉛成分之情況下,仍能在寬電阻範圍下改善溫度特性、電流雜訊、超載特性及靜電放電特性。 The invention relates to a lead-free thick film resistor composition, a lead-free thick film resistor, and a manufacturing method thereof. More specifically, the present invention relates to a lead-free thick-film resistor composition, a lead-free thick-film resistor, and a method for manufacturing the same. The lead-free thick-film resistor composition includes a conductive material containing a ruthenium-based composite oxide and a glass component to form a dual network structure. The composite powder makes it possible to improve the temperature characteristics, current noise, overload characteristics and electrostatic discharge characteristics in a wide range of resistance even without the lead component.
Description
本發明係關於一種無鉛厚膜電阻組合物、一種無鉛厚膜電阻及其製造方法。更具體地,本發明係關於一種無鉛厚膜電阻組合物、無鉛厚膜電阻、及其製造方法,該無鉛厚膜電阻組合物包括藉由包括一釕系複合氧化物及一第一玻璃成分而經熱處理之導電複合粉末、以及一第二玻璃成分以形成雙重網絡結構,使得即使不含鉛成分,仍能在寬電阻範圍下改善溫度特性、電流雜訊、超載特性及靜電放電特性。 The invention relates to a lead-free thick film resistor composition, a lead-free thick film resistor, and a manufacturing method thereof. More specifically, the present invention relates to a lead-free thick-film resistor composition, a lead-free thick-film resistor, and a method of manufacturing the same. The lead-free thick-film resistor composition includes a ruthenium-based composite oxide and a first glass component. The heat-treated conductive composite powder and a second glass component form a dual network structure, so that even without the lead component, the temperature characteristics, current noise, overload characteristics, and electrostatic discharge characteristics can be improved in a wide resistance range.
厚膜電阻組合物一般係由一用於調整電阻值及賦予黏結性(bondability)的玻璃成分、一導電材料、及一由黏著劑及溶劑組成的有機載體所組成。該組合物被印刷在基板上,接著進行燒製以形成厚膜電阻。 The thick film resistor composition is generally composed of a glass component for adjusting the resistance value and imparting bondability, a conductive material, and an organic carrier composed of an adhesive and a solvent. The composition is printed on a substrate and then fired to form a thick film resistor.
許多傳統的厚膜電阻組合物包括作為玻璃材料的氧化鉛系玻璃、及作為導電材料的氧化釕或氧化釕及鉛的化合物,因此,傳統的厚膜電阻組合物含有鉛。 Many conventional thick film resistor compositions include lead oxide-based glass as a glass material, and ruthenium oxide or a compound of ruthenium oxide and lead as a conductive material. Therefore, the conventional thick film resistor composition contains lead.
在彼等厚膜電阻組合物中,氧化釕(RuO2)系厚膜電阻可藉由RuO2及玻璃成分之比例的控制,實現寬範圍的電阻值,且具有優異的電阻溫度係數,且被廣泛地被應用在晶片電阻、併合微電路(hybrid microcircuit)等。 In their thick-film resistor compositions, ruthenium oxide (RuO 2 ) -based thick-film resistors can achieve a wide range of resistance values by controlling the ratio of RuO 2 and glass components, and have excellent resistance temperature coefficients. It is widely used in chip resistors and hybrid microcircuits.
傳統的厚膜電阻係藉由網版印刷法形成在氧化鋁基板上。然而,按照近來電子元件小型化、高頻率、及高功耗的趨勢,存在著由於每單位面積熱放射量增加而使晶片或電路之可靠性及壽命劣化的問題,因此,已改為使用具有優異熱性質的基板,例如氮化鋁基板,來代替氧化鋁基板。一般來說,由於厚膜電阻材料中的玻璃相係用於增加與基板的結合,因此選擇合適的玻璃組合物係非常重要的。目前商業化的用於氧化鋁基板的電阻組合物具有低熔點的包括鉛(Pb)的玻璃組合物。 Traditional thick film resistors are formed on alumina substrates by screen printing. However, according to the recent trend of miniaturization, high frequency, and high power consumption of electronic components, there is a problem that the reliability and life of a chip or a circuit are deteriorated due to an increase in the amount of heat radiation per unit area. Substrates with excellent thermal properties, such as aluminum nitride substrates, instead of aluminum oxide substrates. In general, since the glass phase in the thick film resistance material is used to increase the bonding with the substrate, it is very important to select a suitable glass composition system. Currently commercialized resistance compositions for alumina substrates have low melting point glass compositions including lead (Pb).
然而,最近含鉛玻璃由於環境法規而被禁止,且已知,由於低黏著力、發生起泡(blister)等原因,含鉛玻璃與氮化鋁基板的相互結合性質低。當使用含鉛成分的玻璃時,氧化物,特別是氧化鉛(PbO)會與氮化鋁基板反應,此會造成起泡。低黏著力之其中一原因係當玻璃中的氧化鉛燒結(sinter)時,氧化鉛與氮化鋁反應而還原成鉛(Pb),其中產生氮氣。因此,選擇不包括鉛且具有與氮化鋁良好的相互結合性質的無鉛玻璃組合物係重要的。此外,由於RuO2之電阻溫度係數通常係高達5670ppm/℃,因此需要藉由控制玻璃組合物或者藉由添加具有低電阻溫度係數之成分來努力減少最終厚膜電阻之電阻溫度係數。 However, recently, leaded glass has been banned due to environmental regulations, and it is known that the mutual bonding properties of leaded glass and aluminum nitride substrates are low due to low adhesion, blister, and the like. When using lead-containing glass, oxides, especially lead oxide (PbO), can react with the aluminum nitride substrate, which can cause blistering. One of the reasons for the low adhesion is that when lead oxide in glass is sintered, lead oxide reacts with aluminum nitride to reduce to lead (Pb), and nitrogen is generated therein. Therefore, it is important to select a lead-free glass composition system that does not include lead and has good mutual bonding properties with aluminum nitride. In addition, since the temperature coefficient of resistance of RuO 2 is usually as high as 5670 ppm / ° C, it is necessary to strive to reduce the temperature coefficient of resistance of the final thick film resistance by controlling the glass composition or by adding a component having a low temperature coefficient of resistance.
韓國專利早期公開第10-2006-0056330號(專利文獻 1)揭露了一種電阻膏(resistor paste),其能藉由使用實質上不包括鉛但包括NiO之玻璃材料,提供具有高電阻值及該電阻值之低溫度特性及低短時間超載的電阻。韓國專利早期公開第10-2014-0025338號(專利文獻2)藉由使用具有金紅石(rutile)晶體結構之氧化釕(RuO2)粉末而揭露了一種之用於厚膜電阻之組合物及一種即使在釕含量低的情況下仍具有足夠效能之厚膜電阻。 Korean Patent Early Publication No. 10-2006-0056330 (Patent Document 1) discloses a resistor paste that can provide a high resistance value by using a glass material that substantially does not include lead but includes NiO. Low temperature characteristics of resistance value and low short-term overload resistance. Korean Patent Early Publication No. 10-2014-0025338 (Patent Document 2) discloses a composition for thick film resistance by using a ruthenium oxide (RuO 2 ) powder having a rutile crystal structure and a Thick film resistors with sufficient performance even at low ruthenium content.
當玻璃材料成分改變或當使用具有金紅石晶體結構之氧化釕時,在燒製電阻組合物的時候,顆粒的生長會受到抑制,使得比電阻(specific resistance)降低,厚膜電阻之電阻值的穩定性顯著降低,且如TCR、電流雜訊(C-Noise)等等的電性質也會降低。此外,在製備電阻組合物時,通常僅簡單地將RuO2粉末及玻璃粉末混合,因此,難以獲得成分的均勻混合狀態。因此,難以在燒結之後於厚膜電阻中獲得均勻的微結構。緣此,仍然存在因厚膜電阻之電性質變化增加而使厚膜電阻之穩定性劣化的問題。 When the composition of the glass material is changed or when ruthenium oxide having a rutile crystal structure is used, when the resistance composition is fired, the growth of the particles is suppressed, so that the specific resistance is reduced, and the resistance value of the thick film resistance is reduced. Stability is significantly reduced, and electrical properties such as TCR, current noise (C-Noise), etc. are also reduced. In addition, when preparing a resistance composition, usually, RuO 2 powder and glass powder are simply mixed, and therefore it is difficult to obtain a uniformly mixed state of the components. Therefore, it is difficult to obtain a uniform microstructure in a thick film resistor after sintering. For this reason, there is still a problem that the stability of the thick film resistor is deteriorated due to an increase in the change in the electrical properties of the thick film resistor.
(專利文獻1)韓國專利早期公開第10-2006-0056330號 (Patent Document 1) Korean Patent Early Publication No. 10-2006-0056330
(專利文獻2)韓國專利早期公開第10-2014-0025338號 (Patent Document 2) Korean Patent Early Publication No. 10-2014-0025338
本發明的目的在於提供一種能維持電阻值之穩定性 及電特性之可靠性的無鉛厚膜電阻組合物。更具體地,本發明之一實施態樣旨在提供一種無鉛厚膜電阻組合物,其包括:藉由包括釕系複合氧化物及第一玻璃成分而經熱處理之導電複合粉末、及第二玻璃成分。 An object of the present invention is to provide a lead-free thick film resistor composition capable of maintaining the stability of resistance value and the reliability of electrical characteristics. More specifically, one embodiment of the present invention aims to provide a lead-free thick film resistor composition including: a conductive composite powder that is heat-treated by including a ruthenium-based composite oxide and a first glass component, and a second glass ingredient.
無鉛厚膜電阻組合物形成雙重網絡結構,使得精細的(fine)導電路徑被均勻地形成,因此,本發明之一實施態樣係提供一種無鉛厚膜電阻組合物,其可在即使不包括鉛成分之情況下,在寬電阻範圍下改善溫度特性、電阻分佈、電流雜訊、超載特性、及靜電放電特性,並具有優異穩定性。 The lead-free thick film resistor composition forms a double network structure, so that fine conductive paths are uniformly formed. Therefore, an embodiment of the present invention provides a lead-free thick film resistor composition, which can be used even when lead is not included. In the case of components, it improves temperature characteristics, resistance distribution, current noise, overload characteristics, and electrostatic discharge characteristics over a wide resistance range, and has excellent stability.
此外,本發明另一實施態樣旨在提供一種無鉛厚膜電阻的製造方法。 In addition, another aspect of the present invention is to provide a method for manufacturing a lead-free thick film resistor.
進一步,本發明另一實施態樣旨在提供一種晶片電阻,包括:藉由燒製上述無鉛厚膜電阻組合物所形成之無鉛厚膜電阻。 Further, another aspect of the present invention is to provide a chip resistor, including: a lead-free thick film resistor formed by firing the lead-free thick film resistor composition.
在一般方面,提供一種無鉛厚膜電阻組合物,包括:藉由包括釕系複合氧化物及第一玻璃成分而經熱處理之導電複合粉末;以及第二玻璃成分,其中第一玻璃成分包括SiO2、B2O3、BaO、及Al2O3、且第二玻璃成分包括SiO2、B2O3、及Al2O3。 In a general aspect, a lead-free thick film resistor composition is provided, comprising: a conductive composite powder heat-treated by including a ruthenium-based composite oxide and a first glass component; and a second glass component, wherein the first glass component includes SiO 2 , B 2 O 3 , BaO, and Al 2 O 3 , and the second glass component includes SiO 2 , B 2 O 3 , and Al 2 O 3 .
導電複合粉末可具有結晶結構。 The conductive composite powder may have a crystalline structure.
無鉛厚膜電阻組合物可在燒製後提供雙重網絡結構。 The lead-free thick film resistor composition can provide a dual network structure after firing.
釕系複合氧化物可為選自CaRuO3、BaRuO3、SrRuO3、及(CaxSryBaz)RuO3之任一者或二或更多者之混合物,其中在(CaxSryBaz)RuO3中,需滿足x+y+z=1、0x<1、0y<1、0z<1、以及0<x+y1,第一玻璃成分可更包括選自過渡金屬氧化物、鹼金屬氧化物、及鹼土金屬氧化物之任一者或二或更多者之混合物,且可具有500℃至800℃之軟化點,以及第二玻璃成分可更包括選自過渡金屬氧化物、鹼金屬氧化物、及鹼土金屬氧化物之任一者或二或更多者之混合物,且可具有500℃至700℃之軟化點。 Ruthenium composite oxide may be selected from 3, 3, mixture CaRuO BaRuO SrRuO 3, and (Ca x Sr y Ba z) RuO 3 of any one or two or more of those, where the (Ca x Sr y Ba z ) In RuO 3 , x + y + z = 1, 0 x <1, 0 y <1, 0 z <1, and 0 <x + y 1. The first glass component may further include any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides, and may have a softening point of 500 ° C to 800 ° C. And the second glass component may further include any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides, and may have a softening point of 500 ° C to 700 ° C. .
過渡金屬氧化物可為選自Nb2O5、Ta2O5、TiO2、MnO2、CuO、ZrO2、WO3、及ZnO之任一者或二或更多者之混合物,鹼金屬氧化物可為選自Na2O、K2O、及Li2O之任一者或二或更多者之混合物,以及鹼土金屬氧化物可為選自SrO、CaO、及MgO之任一者或二或更多者之混合物。 The transition metal oxide may be any one or a mixture of two or more selected from Nb 2 O 5 , Ta 2 O 5 , TiO 2 , MnO 2 , CuO, ZrO 2 , WO 3 , and ZnO. The alkali metal is oxidized. The substance may be any one or a mixture of two or more selected from Na 2 O, K 2 O, and Li 2 O, and the alkaline earth metal oxide may be any one selected from SrO, CaO, and MgO or A mixture of two or more.
導電複合粉末可包括20重量%至80重量%之釕系複合氧化物及80重量%至20重量%之第一玻璃成分。 The conductive composite powder may include 20% to 80% by weight of a ruthenium-based composite oxide and 80% to 20% by weight of a first glass component.
導電複合粉末與第二玻璃成分可具有10:90至90:10之重量比。 The conductive composite powder and the second glass component may have a weight ratio of 10:90 to 90:10.
無鉛厚膜電阻組合物可更包括:選自導電粉末及無 機顆粒之任一者或二或更多者之混合物。 The lead-free thick film resistor composition may further include: any one or a mixture of two or more selected from the group consisting of conductive powder and inorganic particles.
無機顆粒可為選自Nb2O5、Ta2O5、TiO2、MnO2、Al2O3、CuO、ZrO2、CoO、BaTiO3、La2O3、Li2TiO3及ZnO之任一者或二或更多者之混合物,以及導電粉末係選自Ag、Au、Pd、Pt、Cu、Ni、W、Mo、Zn、Al、RuO2、IrO2、Rh2O3及AgPd之任一者或二或更多者之混合物。 The inorganic particles may be selected from the group consisting of Nb 2 O 5 , Ta 2 O 5 , TiO 2 , M n O 2 , Al 2 O 3 , CuO, ZrO 2 , CoO, BaTiO 3 , La 2 O 3 , Li 2 TiO 3 and ZnO. Any one or a mixture of two or more, and the conductive powder is selected from the group consisting of Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al, RuO 2 , IrO 2 , Rh 2 O 3 and Any one or a mixture of two or more AgPd.
無鉛厚膜電阻組合物可包括3重量%至65重量%之導電複合粉末、1重量%至60重量%之第二玻璃成分、0.1重量%至40重量%之導電粉末、及0.1重量%至10重量%之無機顆粒。 The lead-free thick film resistor composition may include 3% to 65% by weight of a conductive composite powder, 1% to 60% by weight of a second glass component, 0.1% to 40% by weight of a conductive powder, and 0.1% to 10% by weight. % By weight of inorganic particles.
在另一個一般方面中,提供一種藉由使用上述無鉛厚膜電阻組合物所形成之無鉛厚膜電阻。 In another general aspect, a lead-free thick film resistor formed by using the above-mentioned lead-free thick film resistor composition is provided.
無鉛厚膜電阻,其藉由將上述之無鉛厚膜電阻組合物印刷至一基板上,接著進行燒製所形成。 The lead-free thick film resistor is formed by printing the above-mentioned lead-free thick film resistor composition on a substrate and then firing.
電阻值(Rs)可為10歐姆/□至10兆歐姆/□(MΩ/□)、電阻分佈(CV)可為5%或更低、溫度特性(TCR)可為-100ppm/℃至100ppm/℃、電流雜訊(C-Noise)特性可為12分貝或更低、及在1/8瓦特額定功率下測量之超載特性(STOL)可為0.1%或更低。 The resistance value (Rs) can be 10 ohms / □ to 10 megaohms / □ (MΩ / □), the resistance distribution (CV) can be 5% or lower, and the temperature characteristic (TCR) can be -100ppm / ℃ to 100ppm / ℃, the current noise (C-Noise) characteristic can be 12 dB or lower, and the overload characteristic (STOL) measured at 1/8 watt rated power can be 0.1% or lower.
在另一個一般方面中,提供一種無鉛厚膜電阻的製造方法,包括:(a)藉由熱處理釕系複合氧化物及第一玻璃成分以製造導電複合粉末 (b)製備包括該導電複合粉末及第二玻璃成分之無鉛厚膜電阻組合物;以及(c)藉由燒製該無鉛厚膜電阻組合物以製造具有一雙重網絡結構之無鉛厚膜電阻,其中第一玻璃成分包括SiO2、B2O3、BaO、及Al2O3,及第二玻璃成分包括SiO2、B2O3、及Al2O3。 In another general aspect, a method for manufacturing a lead-free thick film resistor is provided, including: (a) manufacturing a conductive composite powder by heat-treating a ruthenium-based composite oxide and a first glass component; (b) preparing the conductive composite powder including the conductive composite powder and A lead-free thick film resistor composition of a second glass component; and (c) manufacturing a lead-free thick film resistor having a dual network structure by firing the lead-free thick film resistor composition, wherein the first glass component includes SiO 2 , B 2 O 3 , BaO, and Al 2 O 3 , and the second glass component include SiO 2 , B 2 O 3 , and Al 2 O 3 .
在步驟(a)中,該熱處理之溫度係高於600℃且等於或低於900℃,且該導電複合粉末係藉由該熱處理及接著進行之研磨(grinding)而製造。 In step (a), the temperature of the heat treatment is higher than 600 ° C. and equal to or lower than 900 ° C., and the conductive composite powder is manufactured by the heat treatment and subsequent grinding.
在步驟(a)中,該導電複合粉末可藉由熱處理20重量%至80重量%之釕系複合氧化物及80重量%至20重量%之第一玻璃成分而製造,以及在步驟(b)中,在無鉛厚膜電阻組合物中之該導電複合粉末及該第二玻璃成分可具有10:90至90:10之重量比。 In step (a), the conductive composite powder may be manufactured by heat-treating 20 to 80% by weight of a ruthenium-based composite oxide and 80 to 20% by weight of a first glass component, and in step (b) In the lead-free thick film resistor composition, the conductive composite powder and the second glass component may have a weight ratio of 10:90 to 90:10.
在步驟(b)中,無鉛厚膜電阻組合物可更包括選自:導電粉末及無機顆粒之任一者或二或更多者之混合物。 In step (b), the lead-free thick film resistor composition may further include any one or a mixture of two or more selected from the group consisting of conductive powder and inorganic particles.
無鉛厚膜電阻組合物可包括3重量%至65重量%之導電複合粉末、1重量%至60重量%之第二玻璃成分、0.1重量%至40重量%之導電粉末、及0.1重量%至10重量%之無機顆粒。 The lead-free thick film resistor composition may include 3% to 65% by weight of a conductive composite powder, 1% to 60% by weight of a second glass component, 0.1% to 40% by weight of a conductive powder, and 0.1% to 10% by weight. % By weight of inorganic particles.
在另一個一般方面中,提供一種晶片電阻,包括:第一電極、厚膜電阻、及保護用玻璃, 其中厚膜電阻係一無鉛厚膜電阻,其係藉由將上述之無鉛厚膜電阻組合物印刷至一基板上,接著進行燒製而形成。 In another general aspect, a chip resistor is provided, including: a first electrode, a thick film resistor, and a protective glass, wherein the thick film resistor is a lead-free thick film resistor, which is obtained by combining the lead-free thick film resistors described above. An object is printed on a substrate and then formed by firing.
無鉛厚膜電阻組合物包括藉由包括釕系複合氧化物及第一玻璃成分而經熱處理之導電複合粉末、及第二玻璃成分,從而形成雙重網絡結構,使其與傳統的包括鉛的厚膜電阻相比,即使不包括鉛,仍能提供寬電阻值範圍之優異厚膜電阻。此外,無鉛厚膜電阻組合物包括導電複合粉末,使得熱處理時釕系複合氧化物之分解(decomposition)可被抑制,且導電複合粉末之網絡結構可與第二玻璃成分均勻地混合,從而形成雙重網絡結構。因此,可更均勻地形成精細的導電路徑,從而使得提供一種即使在高電阻區下仍沒有特性之劣化,且具非常優異的溫度特性、電流雜訊、超載特性、及靜電放電特性以及優異的穩定性的無鉛厚膜電阻組合物及無鉛厚膜電阻成為可能。 The lead-free thick-film resistor composition includes a conductive composite powder that is heat-treated by including a ruthenium-based composite oxide and a first glass component, and a second glass component to form a dual network structure, which is similar to a conventional thick film including lead. Compared with resistance, even without including lead, it can still provide excellent thick film resistance with wide resistance value range. In addition, the lead-free thick film resistor composition includes a conductive composite powder, so that the decomposition of the ruthenium-based composite oxide can be suppressed during heat treatment, and the network structure of the conductive composite powder can be uniformly mixed with the second glass component, thereby forming a double Network structure. Therefore, a fine conductive path can be formed more uniformly, thereby providing a feature that has no degradation of characteristics even in a high resistance region, and has very excellent temperature characteristics, current noise, overload characteristics, and electrostatic discharge characteristics, and excellent Stable lead-free thick film resistor compositions and lead-free thick film resistors are possible.
第1圖係根據本發明之一例示性實施態樣之無鉛厚膜電阻組合物之印刷圖案及印刷幾何形狀(geometry)之光學顯微鏡影像。 FIG. 1 is an optical microscope image of a printed pattern and a printed geometry of a lead-free thick film resistor composition according to an exemplary embodiment of the present invention.
第2圖係根據本發明之一例示性實施態樣之包括無鉛厚膜電阻之晶片電阻之橫截面圖。 FIG. 2 is a cross-sectional view of a chip resistor including a lead-free thick film resistor according to an exemplary embodiment of the present invention.
第3圖顯示根據本發明之一例示性實施態樣之無鉛厚膜電阻之表面及橫截面之掃描式電子顯微鏡(SEM)之影像。 第3(a)圖顯示電阻之表面、且第3(b)圖顯示電阻之橫截面。 FIG. 3 shows a scanning electron microscope (SEM) image of the surface and cross section of a lead-free thick film resistor according to an exemplary embodiment of the present invention. Figure 3 (a) shows the surface of the resistor, and Figure 3 (b) shows the cross section of the resistor.
第4圖顯示根據本發明之一例示性實施態樣之表2中的複合粉末3之依據熱處理溫度及時間的XRD測量圖。 FIG. 4 shows an XRD measurement chart of the composite powder 3 in Table 2 according to an exemplary embodiment of the present invention according to the heat treatment temperature and time.
第5圖顯示根據本發明之一例示性實施態樣之表2中的複合粉末5之XRD測量圖。 FIG. 5 shows an XRD measurement chart of the composite powder 5 in Table 2 according to an exemplary embodiment of the present invention.
第6圖顯示根據本發明之一例示性實施態樣之表2中的複合粉末13之XRD測量圖。 FIG. 6 shows an XRD measurement chart of the composite powder 13 in Table 2 according to an exemplary embodiment of the present invention.
第7圖顯示根據本發明之一例示性實施態樣之經乾燥塗覆膜與燒製後之無鉛厚膜電阻的XRD測量圖。 FIG. 7 shows an XRD measurement chart of a dried coating film and a lead-free thick film resistance after firing according to an exemplary embodiment of the present invention.
第8圖顯示根據本發明之一例示性實施態樣之在燒製無鉛厚膜電阻組合物後之雙重網絡結構的示意圖。 FIG. 8 is a schematic diagram showing a dual network structure after firing a lead-free thick film resistor composition according to an exemplary embodiment of the present invention.
在下文中,將仔細描述關於無鉛厚膜電阻組合物、無鉛厚膜電阻、及其製造方法之較佳例示性實施態樣及用於測量物理性質的方法。藉由以下實施例可以具體地瞭解本發明,且下方的實施例旨在提供例示說明,而非用於限制由所附本發明請求項所定義的保護範圍。 Hereinafter, preferred exemplary aspects of a lead-free thick film resistor composition, a lead-free thick film resistor, and a manufacturing method thereof, and a method for measuring physical properties will be described in detail. The present invention can be specifically understood through the following examples, and the following examples are intended to provide illustrative illustrations, but not to limit the scope of protection defined by the appended claims of the present invention.
本發明人發現,能夠形成包括藉由包括釕系複合氧化物及第一玻璃成分而經熱處理之導電複合粉末以及第二玻璃成分的無鉛厚膜電阻,由此形成雙重網絡結構,使得精細的導電路徑被均勻地形成,從而即使去除了鉛成分,仍可在寬電阻範圍改善溫度特性、電流雜訊、超載特性、及靜電放電特性,且穩定性 優異,因而完成本發明。 The present inventors have discovered that a lead-free thick film resistor including a conductive composite powder and a second glass component which are heat-treated by including a ruthenium-based composite oxide and a first glass component can be formed, thereby forming a dual network structure and making fine conductive The paths are formed uniformly, so that even if the lead component is removed, the temperature characteristics, current noise, overload characteristics, and electrostatic discharge characteristics can be improved over a wide resistance range, and the stability is excellent, and the present invention has been completed.
於本文中,術語「雙重網絡結構」意思係藉由熱處理釕系複合氧化物及第一玻璃成分而獲得之導電複合粉末具有初級網絡結構,此為第一網絡,以及第二玻璃成分被燒製並因此次要地形成次級網絡,從而形成雙重網絡結構,這表示所形成的導電路徑比初級網絡結構更為緻密。 As used herein, the term "dual network structure" means that a conductive composite powder obtained by heat-treating a ruthenium-based composite oxide and a first glass component has a primary network structure. This is the first network, and the second glass component is fired. Therefore, a secondary network is formed secondaryly, thereby forming a dual network structure, which means that the conductive path formed is denser than the primary network structure.
於本文中,術語「無鉛」意思係厚膜電阻的鉛成分含量係1000ppm或更低,較佳500ppm或更低。 As used herein, the term "lead-free" means that the lead content of the thick film resistor is 1000 ppm or less, preferably 500 ppm or less.
在下文中,將詳細描述本發明的例示性實施態樣。 Hereinafter, exemplary embodiments of the present invention will be described in detail.
根據本發明之一例示性實施態樣,無鉛厚膜電阻組合物可包括導電複合粉末及第二玻璃成分。 According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include a conductive composite powder and a second glass component.
根據本發明之一例示性實施態樣,無鉛厚膜電阻組合物可包括導電複合粉末、第二玻璃成分、導電粉末、及無機顆粒。 According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include a conductive composite powder, a second glass component, a conductive powder, and inorganic particles.
由於初級網絡(導電複合粉末的第一網絡)及第二玻璃成分,可形成一其中形成有次級網絡的穩定雙重網絡結構,從而可在即使不包括鉛的情況下,均勻地形成精細的導電路徑,以提供具寬電阻值範圍的優異厚膜電阻。 Due to the primary network (the first network of the conductive composite powder) and the second glass component, a stable dual network structure with a secondary network formed therein can be formed, so that fine conductive can be formed uniformly even without including lead Path to provide excellent thick film resistance with a wide range of resistance values.
根據本發明之一例示性實施態樣,導電複合粉末可藉由包括釕系複合氧化物及第一玻璃成分的熱處理所製造。當傳統的釕系複合氧化物被單獨採用時,XRuO3被分解成XO及RuO2,比電阻會被降低,且待製造的厚膜電阻的電阻值的穩定性會顯著 地降低,且難以維持例如溫度特性(TCR)、電流雜訊(C-Noise)等電性質。在XRuO3及XO中,X為Ca、Sr、Ba等。為了解決這些問題,可以瞭解的是,當使用藉由熱處理具有鈣鈦礦(perovskite)結構之釕系複合氧化物及第一玻璃成分所獲得的導電複合粉末時,可形成穩定網絡結構。 According to an exemplary embodiment of the present invention, the conductive composite powder may be manufactured by a heat treatment including a ruthenium-based composite oxide and a first glass component. When the traditional ruthenium-based composite oxide is used alone, XRuO 3 is decomposed into XO and RuO 2 , the specific resistance is reduced, and the stability of the resistance value of the thick film resistor to be manufactured is significantly reduced, and it is difficult to maintain Such as temperature characteristics (TCR), current noise (C-Noise) and other electrical properties. In XRuO 3 and XO, X is Ca, Sr, Ba, or the like. In order to solve these problems, it is understood that when a conductive composite powder obtained by heat-treating a ruthenium-based composite oxide having a perovskite structure and a first glass component is used, a stable network structure can be formed.
根據本發明之一例示性實施態樣,釕系複合氧化物並無限制,只要其是具有本領域中所熟知的鈣鈦礦晶體結構的釕系複合氧化物即可。舉例而言,釕系複合氧化物可選自釕酸鈣(CaRuO3)、釕酸鍶(SrRuO3)、釕酸鋇(BaRuO3)、及(CaxSryBaz)RuO3之任一者或二或更多者之混合物,其中在(CaxSryBaz)RuO3中,需滿足x+y+z=1、0x<1、0y<1、0z<1、以及0<x+y1。例如,也可使用(CaxSry)RuO3、(SryBaz)RuO3、或(CaxBaz)RuO3。第一玻璃成分更包括選自過渡金屬氧化物、鹼金屬氧化物、及鹼土金屬氧化物之任一者或二或更多者之混合物。此外,導電複合粉末可藉由在釕系複合氧化物及第一玻璃成分之外更包括釕氧化物、導電金屬氧化物、及金屬成分而獲得。 According to an exemplary embodiment of the present invention, the ruthenium-based composite oxide is not limited as long as it is a ruthenium-based composite oxide having a perovskite crystal structure well known in the art. For example, ruthenium-based composite oxide according to any one selected from calcium ruthenate (CaRuO 3), strontium ruthenate (SrRuO 3), barium ruthenate (BaRuO 3), and (Ca x Sr y Ba z) RuO 3 of Or a mixture of two or more of them, in (Ca x Sr y Ba z ) RuO 3 , x + y + z = 1, 0 x <1, 0 y <1, 0 z <1, and 0 <x + y 1. For example, (Ca x Sr y ) RuO 3 , (Sr y Ba z ) RuO 3 , or (Ca x Ba z ) RuO 3 may be used . The first glass component further includes any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides. In addition, the conductive composite powder can be obtained by including a ruthenium oxide, a conductive metal oxide, and a metal component in addition to the ruthenium-based composite oxide and the first glass component.
具有鈣鈦礦晶體結構的釕系複合氧化物是有效用的,因為其用於特別是在1KΩ或更高時維持溫度特性(TCR)及超載(STOL)。 A ruthenium-based composite oxide having a perovskite crystal structure is effective because it is used to maintain temperature characteristics (TCR) and overload (STOL) especially at 1 KΩ or higher.
根據本發明之一例示性實施態樣的釕系複合氧化物可具有10平方公尺/公克或更多之比表面積,更佳具有10平方公尺/公克至80平方公尺/公克之比表面積,但不限於此。 The ruthenium-based composite oxide according to an exemplary embodiment of the present invention may have a specific surface area of 10 square meters / g or more, and more preferably a specific surface area of 10 square meters / g to 80 square meters / gram. , But not limited to this.
根據本發明之一例示性實施態樣的釕系複合氧化物並無限制,但可藉由在韓國專利第10-0840893號中所述之製造方法製造。 The ruthenium-based composite oxide according to an exemplary embodiment of the present invention is not limited, but can be manufactured by the manufacturing method described in Korean Patent No. 10-0840893.
舉例而言,1)釕鹽水溶液可藉由將釕金屬粉末溶在強酸或強鹼中或者藉由釕金屬粉末之鹼熔(alkali fusion)而成。2)已製備的釕鹽水溶液可與含有分散劑的鍶化合物水溶液混合以獲得釕酸鍶水合物。3)已獲得的釕酸鍶水合物可在300℃至1500℃下進行熱處理以獲得釕酸鍶粉末。4)可將無機酸加至已獲得的釕酸鍶粉末以移除雜質。然而,釕鹽水溶液之製備係不限於此。 For example, 1) the ruthenium salt aqueous solution can be formed by dissolving a ruthenium metal powder in a strong acid or a strong base or by an alkali fusion of the ruthenium metal powder. 2) The prepared ruthenium salt aqueous solution may be mixed with a dispersant-containing strontium compound aqueous solution to obtain strontium ruthenate hydrate. 3) The obtained strontium ruthenate hydrate can be heat-treated at 300 ° C to 1500 ° C to obtain strontium ruthenate powder. 4) An inorganic acid may be added to the obtained strontium ruthenate powder to remove impurities. However, the preparation of the ruthenium salt aqueous solution is not limited thereto.
更具體地,為了製備釕鹽水溶液,將氧化劑加入至強鹼水溶液或強酸水溶液,並將釕化合物加入其中,接著攪拌,使得釕可被氧化以獲得一猩紅釕酸鹽(scarlet ruthenate)水溶液。該釕化合物並無限制,但作為釕化合物,可使用氯化釕、硫酸釕或釕金屬海綿(ruthenium metal sponge),且較佳可使用釕金屬海綿。 More specifically, in order to prepare an aqueous ruthenium salt solution, an oxidizing agent is added to a strong alkaline aqueous solution or a strong acid aqueous solution, and a ruthenium compound is added thereto, followed by stirring, so that ruthenium can be oxidized to obtain a scarlet ruthenate aqueous solution. The ruthenium compound is not limited, but as the ruthenium compound, ruthenium chloride, ruthenium sulfate, or a ruthenium metal sponge can be used, and a ruthenium metal sponge is preferably used.
作為酸,可使用選自鹽酸、硝酸、及硫酸等之任一者或二或更多者之混合物,或者較佳可使用包括重量比為3:1至1:1之鹽酸及硝酸的王水;而作為鹼,可使用氫氧化鈉或氫氧化鉀。氧化劑可為次氯酸鈉或硝酸鉀,但不限於此。 As the acid, any one or a mixture of two or more selected from hydrochloric acid, nitric acid, and sulfuric acid may be used, or preferably aqua regia including hydrochloric acid and nitric acid in a weight ratio of 3: 1 to 1: 1 ; As the base, sodium hydroxide or potassium hydroxide can be used. The oxidant may be, but is not limited to, sodium hypochlorite or potassium nitrate.
此外,釕鹽水溶液可甚至藉由使用鹼性鹽之鹼熔所獲得。根據鹼熔,釕金屬海綿係與一其中氫氧化鉀與氫氧化鈉以3:1至1:3之重量比混合的水溶液混合,且在400℃至800℃加熱,接著以強酸瀝濾(leach)以獲得釕鹽。釕金屬海綿係具有在顆粒 及粉末之間之中等尺寸的釕金屬,且可用作製備釕鹽的起始物。釕酸水溶液每1公升(L)之釕濃度適當地係小於50公克/公升,且在鹼溶解(alkali dissolution)中用於溶解釕之溫度較佳為20℃至100℃,但不限於此。 In addition, the ruthenium salt aqueous solution can be obtained even by alkali melting using a basic salt. According to alkali melting, the ruthenium metal sponge is mixed with an aqueous solution in which potassium hydroxide and sodium hydroxide are mixed in a weight ratio of 3: 1 to 1: 3, and heated at 400 ° C to 800 ° C, followed by leaching with a strong acid (leach ) To obtain a ruthenium salt. The ruthenium metal sponge is a ruthenium metal having an equal size between particles and powder, and can be used as a starting material for preparing a ruthenium salt. The ruthenium concentration per liter (L) of the ruthenium acid aqueous solution is suitably less than 50 g / liter, and the temperature for dissolving ruthenium in alkali dissolution is preferably 20 ° C to 100 ° C, but is not limited thereto.
根據本發明之一例示性實施態樣,第一玻璃成分可包括SiO2、B2O3、BaO及Al2O3。具有以上組合之第一玻璃成分是有效的,因為其易於與釕系複合氧化物產生錯合。 According to an exemplary embodiment of the present invention, the first glass component may include SiO 2 , B 2 O 3 , BaO, and Al 2 O 3 . The first glass component having the above combination is effective because it is liable to cause a mismatch with the ruthenium-based composite oxide.
進一步,第一玻璃成分可包括SiO2、B2O3、BaO及Al2O3作為主要成分,其對於更加改善與釕系複合氧化物之反應性,以使網絡結構更緻密地形成是較佳的,且進一步,其可有效地在製備導電複合粉末時改善與第二玻璃成分之相容性。彼等主要成分可以至少50重量%,更具體而言50重量%至99重量%的含量被包括在第一玻璃成分中。尤其,藉由含有BaO之第一玻璃成分及釕系複合氧化物之錯合所獲得的導電複合粉末,可防止因釕複合氧化物與第二玻璃成分反應而生成氧化釕,從而可形成更穩定的晶體結構。本發明中的晶體結構包括Ba-Si-Al系部分晶體結構或整體晶體結構。當使用具有穩定晶體結構之導電複合粉末來製備導電厚膜電阻組合物時,可以藉由在燒製過程中之釕系複合氧化物及第二玻璃成分之反應來控制釕氧化物之生成,從而獲得一電性質更穩定的厚膜電阻是可能的,因為如第7圖所示,出於燒製的晶體結構變化是小的。 Further, the first glass component may include SiO 2 , B 2 O 3 , BaO, and Al 2 O 3 as main components, which is more effective for improving the reactivity with the ruthenium-based composite oxide and making the network structure more densely formed. It is good, and further, it can effectively improve the compatibility with the second glass component when preparing the conductive composite powder. Their main components may be included in the first glass component in an amount of at least 50% by weight, more specifically, 50% to 99% by weight. In particular, the conductive composite powder obtained by the combination of the first glass component containing BaO and the ruthenium-based composite oxide can prevent the formation of ruthenium oxide due to the reaction between the ruthenium composite oxide and the second glass component, and thus can form a more stable Crystal structure. The crystal structure in the present invention includes a Ba-Si-Al-based partial crystal structure or an overall crystal structure. When using a conductive composite powder with a stable crystal structure to prepare a conductive thick film resistor composition, the formation of ruthenium oxide can be controlled by the reaction of the ruthenium-based composite oxide and the second glass component during firing, thereby It is possible to obtain a thick film resistor with more stable electrical properties, because as shown in Fig. 7, the change in the crystal structure due to firing is small.
根據本發明之一例示性實施態樣的第一玻璃成分之具體組成可包括,例如10重量%至40重量%之SiO2、10重量%至30 重量%之B2O3、5重量%至40重量%之BaO、2重量%至15重量%之Al2O3、0.1重量%至20重量%之過渡金屬氧化物、及20重量%至60重量%之鹼金屬氧化物與鹼土金屬氧化物。較佳地,第一玻璃成分可包括15重量%至30重量%之SiO2、15重量%至30重量%之B2O3、10重量%至30重量%之BaO、5重量%至15重量%之Al2O3、5重量%至15重量%之過渡金屬氧化物、及20重量%至40重量%之鹼金屬氧化物與鹼土金屬氧化物,但不限於此。具有上述範圍的第一玻璃成分對於與釕系複合氧化物具有優異的反應性以及改善電性質及耐久性是有效的。 A specific composition of the first glass component according to an exemplary embodiment of the present invention may include, for example, 10% to 40% by weight of SiO 2 , 10% to 30% by weight of B 2 O 3 , 5% to 40% by weight of BaO, 2% by weight to 15% by weight of Al 2 O 3 , 0.1% by weight to 20% by weight of transition metal oxides, and 20% by weight to 60% by weight of alkali metal oxides and alkaline earth metal oxides . Preferably, the first glass component may include 15 to 30% by weight of SiO 2 , 15 to 30% by weight of B 2 O 3 , 10 to 30% by weight of BaO, and 5 to 15% by weight. % Al 2 O 3 , 5% to 15% by weight of transition metal oxides, and 20% to 40% by weight of alkali metal oxides and alkaline earth metal oxides, but are not limited thereto. The first glass component having the above range is effective for having excellent reactivity with the ruthenium-based composite oxide and improving electrical properties and durability.
根據本發明之一例示性實施態樣,第一玻璃成分可包括選自過渡金屬氧化物、鹼金屬氧化物、及鹼土金屬氧化物之任一者或二或更多者之混合物。 According to an exemplary embodiment of the present invention, the first glass component may include any one or a mixture of two or more selected from transition metal oxides, alkali metal oxides, and alkaline earth metal oxides.
第一玻璃成分中的過渡金屬氧化物可添加用來控制溫度特性(TCR)、超載特性(STOL)、及靜電放電特性(ESD),且可包括鹼金屬氧化物及鹼土金屬氧化物以改善與釕系複合氧化物之反應性。 The transition metal oxide in the first glass component may be added to control temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD), and may include alkali metal oxides and alkaline earth metal oxides to improve and Reactivity of ruthenium-based composite oxides.
根據本發明之一例示性實施態樣,過渡金屬氧化物並無限制,只要其是本領域中所熟知的過渡金屬氧化物即可。過渡金屬氧化物可為例如選自Nb2O5、Ta2O5、TiO2、MnO2、CuO、ZrO2、WO3及ZnO之任一者或二或更多者之混合物,但不限於此。 According to an exemplary embodiment of the present invention, the transition metal oxide is not limited as long as it is a transition metal oxide well known in the art. The transition metal oxide may be, for example, any one or a mixture of two or more selected from the group consisting of Nb 2 O 5 , Ta 2 O 5 , TiO 2 , MnO 2 , CuO, ZrO 2 , WO 3 and ZnO. this.
根據本發明之一例示性實施態樣,鹼金屬氧化物並無限制,只要其是本領域所熟知的鹼金屬氧化物即可。鹼金屬氧化物可為選自Na2O、K2O及Li2O之任一者或二或更多者之混合 物,但不限於此。 According to an exemplary embodiment of the present invention, the alkali metal oxide is not limited as long as it is an alkali metal oxide well known in the art. The alkali metal oxide may be any one selected from Na 2 O, K 2 O, and Li 2 O, or a mixture of two or more, but is not limited thereto.
根據本發明之一例示性實施態樣,鹼土金屬氧化物並無限制,只要其是本領域中所熟知的鹼土金屬氧化物即可。鹼土金屬氧化物可為選自SrO、CaO、及MgO之任一者或二或更多者之混合物,但不限於此。 According to an exemplary embodiment of the present invention, the alkaline earth metal oxide is not limited as long as it is an alkaline earth metal oxide well known in the art. The alkaline earth metal oxide may be any one selected from SrO, CaO, and MgO or a mixture of two or more, but is not limited thereto.
根據本發明之一例示性實施態樣,第一玻璃成分可具有500℃至800℃之軟化點,以形成均勻的網絡。軟化點在上述範圍的第一玻璃成分是較佳的,因為與釕系複合氧化物之反應性可被改良以更均勻地形成初級網絡,該初級網絡為第一網絡,且在熱處理過程中可產生具有部分晶體結構之經熱處理導電複合粉末。 According to an exemplary embodiment of the present invention, the first glass component may have a softening point of 500 ° C. to 800 ° C. to form a uniform network. The first glass component having a softening point in the above range is preferable because the reactivity with the ruthenium-based composite oxide can be improved to more uniformly form a primary network, which is the first network and can be formed during heat treatment. A heat-treated conductive composite powder having a partially crystalline structure was produced.
進一步,第二玻璃成分可具有500℃至700℃之軟化點。當第二玻璃成分的軟化點在上述範圍是較佳的,因為在700℃至900℃的燒製溫度形成雙重網絡是容易的,且可改善無鉛厚膜電阻的表面均勻度以降低變異係數(CV),從而具有優異電性質。可根據氧化鋇是否存在來控制上述第一玻璃成分及第二玻璃成分的不同軟化點。由於第二玻璃成分不包括氧化鋇,因此可防止在形成雙重網絡的期間,因為與基板之高反應性,而使變異係數(CV)增高的現象。 Further, the second glass component may have a softening point of 500 ° C to 700 ° C. When the softening point of the second glass component is in the above range, it is easy to form a dual network at a firing temperature of 700 ° C to 900 ° C, and the surface uniformity of the lead-free thick film resistor can be improved to reduce the coefficient of variation ( CV), which has excellent electrical properties. The different softening points of the first glass component and the second glass component can be controlled according to the presence or absence of barium oxide. Since the second glass component does not include barium oxide, it is possible to prevent the phenomenon of increasing the coefficient of variation (CV) due to the high reactivity with the substrate during the formation of the double network.
根據本發明之一例示性實施態樣,導電複合粉末可藉由在特定熱處理溫度範圍下熱處理釕系複合氧化物及第一玻璃成分之混合物,接著進行研磨而粒化。導電複合粉末的平均粒徑並無限制。舉例而言,當從小顆粒累積至一量時,相應於總量的 50%之顆粒直徑D50可為2.0微米或更小。較佳地,D50可為1.0微米至2.0微米。根據上述範圍的研磨是有效的,因為在厚膜電阻組合物中導電複合粉末可輕易與第二玻璃成分混合以提供一均勻的組合物。 According to an exemplary embodiment of the present invention, the conductive composite powder may be granulated by heat-treating a mixture of a ruthenium-based composite oxide and a first glass component at a specific heat treatment temperature range, followed by grinding. The average particle diameter of the conductive composite powder is not limited. For example, when accumulated from small particles to an amount, the particle diameter D50 corresponding to 50% of the total amount may be 2.0 microns or less. Preferably, D50 can be 1.0 micrometer to 2.0 micrometer. Grinding according to the above range is effective because the conductive composite powder can be easily mixed with the second glass component in the thick film resistor composition to provide a uniform composition.
熱處理溫度並無限制,只要其是本領域中所熟知之厚膜電阻組合物的熱處理溫度或更高的溫度即可,且舉例而言,其較佳可高於600℃且等於或低於900℃,且可在該熱處理溫度下在120分鐘內進行熱處理。 The heat treatment temperature is not limited as long as it is a heat treatment temperature or higher of a thick film resistor composition known in the art, and for example, it is preferably higher than 600 ° C and equal to or lower than 900 ℃, and the heat treatment can be performed within 120 minutes at the heat treatment temperature.
如上所形成之導電複合粉末可形成均勻的初級網絡結構,該初級網絡結構為第一網絡結構。在製造無鉛厚膜電阻時,釕系複合氧化物及第一玻璃成分透過熱處理形成為第一網絡的初級網絡,且釕系複合氧化物及第二玻璃成分之間的反應性可受到抑制,因此不會發生釕系複合氧化物的分解,從而形成更穩定的雙重網絡結構。 The conductive composite powder formed as described above can form a uniform primary network structure, and the primary network structure is a first network structure. When manufacturing lead-free thick film resistors, the ruthenium-based composite oxide and the first glass component are formed into a primary network of the first network through heat treatment, and the reactivity between the ruthenium-based composite oxide and the second glass component can be suppressed, so Decomposition of the ruthenium-based composite oxide does not occur, thereby forming a more stable dual network structure.
根據本發明之一例示性實施態樣,導電複合粉末可包括20重量%至80重量%之釕系複合氧化物及80重量%至20重量%之第一玻璃成分,更佳30重量%至70重量%之釕系複合氧化物及70重量%至30重量%之第一玻璃成分。更佳地,導電複合粉末可包括40重量%至60重量%之釕系複合氧化物及60重量%至40重量%之第一玻璃成分。 According to an exemplary embodiment of the present invention, the conductive composite powder may include 20 to 80% by weight of a ruthenium-based composite oxide and 80 to 20% by weight of a first glass component, and more preferably 30 to 70% by weight. The ruthenium-based composite oxide is 70% by weight and the first glass component is 70% to 30% by weight. More preferably, the conductive composite powder may include 40% to 60% by weight of a ruthenium-based composite oxide and 60% to 40% by weight of a first glass component.
當釕系複合氧化物及第一玻璃成分係包括在上述範圍中時是有效的,因為可容易形成為第一網絡的初級網絡結構,且容易控制溫度特性(TCR)、超載特性(STOL)、及靜電放電特 性(ESD)。 It is effective when the ruthenium-based composite oxide and the first glass component system are included in the above range, because it can be easily formed into a primary network structure of the first network, and it is easy to control temperature characteristics (TCR), overload characteristics (STOL), And electrostatic discharge characteristics (ESD).
此外,當釕系複合氧化物及第一玻璃成分係包括在上述範圍中時,可獲得低的電阻值,可防止溫度特性沿(-)方向移動、且(+)之溫度特性不呈現作為導電材料之最佳比電阻之情況,並較佳地維持晶體結構之穩定性。 In addition, when the ruthenium-based composite oxide and the first glass component system are included in the above range, a low resistance value can be obtained, the temperature characteristic can be prevented from moving in the (-) direction, and the temperature characteristic of (+) does not appear as conductive The best specific resistance of the material, and the stability of the crystal structure is better maintained.
根據本發明之一例示性實施態樣,第二玻璃成分可包括SiO2、B2O3及Al2O3作為主要成分,且可更包括選自過渡金屬氧化物、鹼金屬氧化物、及鹼土金屬氧化物之任一者或二或更多者之混合物。該等主要成分可以至少40重量%,更具體而言40重量%至99重量%之含量包括在第二玻璃成分中。 According to an exemplary embodiment of the present invention, the second glass component may include SiO 2 , B 2 O 3, and Al 2 O 3 as main components, and may further include a member selected from transition metal oxides, alkali metal oxides, and Any one or a mixture of two or more alkaline earth metal oxides. These main components may be included in the second glass component in an amount of at least 40% by weight, more specifically, 40% to 99% by weight.
根據本發明之一例示性實施態樣,第二玻璃成分之的具體組成可包括,例如10重量%至30重量%之SiO2、10重量%至40重量%之B2O3、2重量%至15重量%之Al2O3、0.1重量%至10重量%之過渡金屬氧化物、及20重量%至60重量%之鹼金屬氧化物與鹼土金屬氧化物。較佳地,第二玻璃成分可包括10重量%至20重量%之SiO2、20重量%至40重量%之B2O3、2重量%至10重量%之Al2O3、0.1重量%至10重量%之過渡金屬氧化物、及30重量%至60重量%之鹼金屬氧化物與鹼土金屬氧化物,但不限於此。第二玻璃成分具有在上述含量範圍中的上述成分,可有效地與導電複合粉末具有優異的相容性及錯合,且可有效改善電性質及耐久性。 According to an exemplary embodiment of the present invention, the specific composition of the second glass component may include, for example, 10% to 30% by weight of SiO 2 , 10% to 40% by weight of B 2 O 3 , 2% by weight To 15% by weight of Al 2 O 3 , 0.1% to 10% by weight of transition metal oxides, and 20% to 60% by weight of alkali metal oxides and alkaline earth metal oxides. Preferably, the second glass component may include 10 to 20% by weight of SiO 2 , 20 to 40% by weight of B 2 O 3 , 2 to 10% by weight of Al 2 O 3 , and 0.1% by weight. To 10% by weight of transition metal oxides, and 30% to 60% by weight of alkali metal oxides and alkaline earth metal oxides, but are not limited thereto. The second glass component has the above-mentioned components in the above-mentioned content range, can effectively have excellent compatibility and mismatch with the conductive composite powder, and can effectively improve electrical properties and durability.
當第二玻璃成分之構成具有上述範圍時,第二玻璃成分之穩定性可為優異的且可防止軟化點的增高。當穩定性係優異時係較佳的,因為此可改善塗覆膜之厚膜電阻之塗覆膜強度, 無鉛厚膜電阻之電性質可在用於形成第一電極及在晶片電阻保護用之玻璃的過程中獲得改善。 When the composition of the second glass component has the above range, the stability of the second glass component can be excellent and an increase in the softening point can be prevented. It is better when the stability is excellent, because this can improve the coating film strength of the thick film resistor. The electrical properties of the lead-free thick film resistor can be used to form the first electrode and to protect the chip resistance. The glass process was improved.
因此,根據上述構成之組合之第二玻璃成分係有效的,因為其可維持無鉛厚膜電阻之密度及光滑塑性表面(smooth plastic surface)並且與導電複合粉末形成均勻且緻密的雙重網絡結構。 Therefore, the second glass composition according to the combination of the above constitutions is effective because it can maintain the density and smooth plastic surface of the lead-free thick film resistor and form a uniform and dense double network structure with the conductive composite powder.
可加入過渡金屬氧化物,以控制溫度特性(TCR)、超載特性(STOL)、及靜電放電特性(ESD),且可包括鹼土金屬氧化物,以改善與釕系複合氧化物之反應性。尤其,可將鹼金屬氧化物加入至第二玻璃成分以改善玻璃成分與其他成分組合之流動性。 Transition metal oxides can be added to control temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD), and can include alkaline earth metal oxides to improve reactivity with ruthenium-based composite oxides. In particular, an alkali metal oxide may be added to the second glass component to improve the fluidity of the glass component in combination with other components.
根據本發明之一例示性實施態樣的過渡金屬氧化物並無限制,只要其是本領域中所熟知的過渡金屬氧化物即可。過渡金屬氧化物可為例如選自Nb2O5、Ta2O5、TiO2、MnO2、CuO、ZrO2、WO3及ZnO之任一者或二或更多者之混合物,但不限於此。 The transition metal oxide according to an exemplary embodiment of the present invention is not limited as long as it is a transition metal oxide well known in the art. The transition metal oxide may be, for example, any one or a mixture of two or more selected from the group consisting of Nb 2 O 5 , Ta 2 O 5 , TiO 2 , MnO 2 , CuO, ZrO 2 , WO 3 and ZnO. this.
根據本發明之一例示性實施態樣,鹼金屬氧化物並無限制,只要其是本領域中所熟知的鹼金屬氧化物即可。鹼金屬氧化物可為選自Na2O、K2O及Li2O之任一者或二或更多者之混合物,但不限於此。 According to an exemplary embodiment of the present invention, the alkali metal oxide is not limited as long as it is an alkali metal oxide well known in the art. The alkali metal oxide may be any one selected from Na 2 O, K 2 O, and Li 2 O, or a mixture of two or more, but is not limited thereto.
根據本發明之一例示性實施態樣,鹼土金屬氧化物並無限制,只要其是本領域中所熟知的鹼土金屬氧化物即可。鹼土金屬氧化物可為選自SrO、CaO及MgO之任一者或二或更多者之 混合物,但不限於此。 According to an exemplary embodiment of the present invention, the alkaline earth metal oxide is not limited as long as it is an alkaline earth metal oxide well known in the art. The alkaline earth metal oxide may be any one selected from SrO, CaO, and MgO or a mixture of two or more, but is not limited thereto.
根據本發明之一例示性實施態樣,在步驟(c)之700℃至900℃之燒製溫度中,第二玻璃成分較佳具有500℃至700℃之軟化點,以與導電複合粉末形成均勻網絡並改善厚膜電阻之密度,但軟化點並不限於此。 According to an exemplary embodiment of the present invention, in the firing temperature of 700 ° C. to 900 ° C. in step (c), the second glass component preferably has a softening point of 500 ° C. to 700 ° C. to form a conductive composite powder. Uniform network and improve the density of thick film resistance, but the softening point is not limited to this.
根據本發明之一例示性實施態樣,無鉛厚膜電阻組合物可包括在10:90至90:10之重量比的導電複合粉末及第二玻璃成分,更佳在20:80至80:20之重量比的導電複合粉末及第二玻璃成分。 According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include a conductive composite powder and a second glass component in a weight ratio of 10:90 to 90:10, and more preferably 20:80 to 80:20. Weight ratio of the conductive composite powder and the second glass component.
當導電複合粉末及第二玻璃成分係包括在上述範圍中時是有效的,因為其可容易形成雙重網絡結構,且容易控制溫度特性(TCR)、超載特性(STOL)、及靜電放電特性(ESD)。 It is effective when the conductive composite powder and the second glass component are included in the above range, because it can easily form a dual network structure, and it is easy to control temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD) ).
此外,當導電複合粉末及第二玻璃成分係包括在上述範圍中時係較佳的,因為藉由具有上述範圍之無鉛厚膜電阻組合物所製備之無鉛厚膜電阻之電性質可被改善,且可形成均勻的無鉛厚膜電阻。 In addition, it is preferable when the conductive composite powder and the second glass component are included in the above range, because the electrical properties of the lead-free thick film resistor prepared by the lead-free thick film resistor composition having the above range can be improved, And can form a uniform lead-free thick film resistor.
在無鉛厚膜電阻之物理性質不受到妨礙的範圍內,無鉛厚膜電阻組合物可更包括導電粉末及無機顆粒,以增加導電路徑。 To the extent that the physical properties of the lead-free thick film resistor are not impeded, the lead-free thick film resistor composition may further include conductive powder and inorganic particles to increase the conductive path.
導電粉末並無限制,只要其是本領域中所熟知的導電粉末即可,舉例而言,可更包括選自Ag、Au、Pd、Pt、Cu、Ni、W、Mo、Zn、Al、RuO2、IrO2、Rh2O3及AgPd之任一者或二或更 多者之混合物。 The conductive powder is not limited as long as it is a conductive powder well known in the art, for example, it may further include a member selected from the group consisting of Ag, Au, Pd, Pt, Cu, Ni, W, Mo, Zn, Al, RuO 2. Any one or a mixture of two or more of IrO 2 , Rh 2 O 3 and AgPd.
進一步,無鉛厚膜電阻組合物可更包括無機顆粒,以控制溫度特性(TCR)、超載特性(STOL)、及靜電放電特性(ESD)。 Further, the lead-free thick film resistor composition may further include inorganic particles to control temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD).
根據本發明之一例示性實施態樣,無機顆粒可選自Nb2O5、Ta2O5、TiO2、MnO2、Al2O3、CuO、ZrO2、CoO、BaTiO3、La2O3、Li2TiO3、ZnO及WO3之任一者或二或更多者之混合物,但不限於此。 According to an exemplary embodiment of the present invention, the inorganic particles may be selected from Nb 2 O 5 , Ta 2 O 5 , TiO 2 , MnO 2 , Al 2 O 3 , CuO, ZrO 2 , CoO, BaTiO 3 , La 2 O 3. Any one or a mixture of two or more of Li 2 TiO 3 , ZnO, and WO 3 , but is not limited thereto.
根據本發明之一例示性實施態樣,無鉛厚膜電阻組合物可包括,舉例而言,3重量%至65重量%之導電複合粉末、1重量%至60重量%之第二玻璃成分、0.1重量%至40重量%之導電粉末、及0.1重量%至10重量%之無機顆粒,但無鉛厚膜電阻組合物之各個含量係不限於此。較佳地,無鉛厚膜電阻組合物可包括25重量%至60重量%之導電複合粉末、20重量%至60重量%之第二玻璃成分、1重量%至20重量%之導電粉末、及0.1重量%至5重量%之無機顆粒。 According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include, for example, 3% to 65% by weight of a conductive composite powder, 1% to 60% by weight of a second glass component, 0.1 The conductive powder is from 40% by weight to 40% by weight, and the inorganic particles are from 0.1% to 10% by weight, but each content of the lead-free thick film resistor composition is not limited thereto. Preferably, the lead-free thick film resistor composition may include 25% to 60% by weight of a conductive composite powder, 20% to 60% by weight of a second glass component, 1% to 20% by weight of a conductive powder, and 0.1. Weight percent to 5 weight percent of inorganic particles.
無鉛厚膜電阻組合物具有上述含量範圍,使得雙重網絡結構可容易地形成。由於雙重網絡結構的形成,能夠獲得電阻分佈(CV)、及電阻再現性係優異,且溫度特性(TCR)、超載特性(STOL)、及靜電放電特性(ESD)係優異。 The lead-free thick film resistor composition has the above-mentioned content range, so that a dual network structure can be easily formed. Due to the formation of the dual network structure, excellent resistance distribution (CV) and resistance reproducibility are obtained, and temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD) are excellent.
根據本發明之一例示性實施態樣,無鉛厚膜電阻組合物可更包括由有機溶劑及黏著劑組成之載體。為了混合導電複 合粉末及第二玻璃成分且將該混合物施用至網版印刷等,且將該混合物做為用於形成各自具有適合的流變性之膏(paste)、塗料(paint)、墨水的組合物,可混合一般的載體。載體並無限制,只要其是本領域中所熟知的載體即可。舉例而言,載體可為混合以下成分之溶液:萜品醇(terpineol)、卡必醇、丁卡必醇、賽珞蘇、丁賽珞蘇、或其酯;選自甲苯、二甲苯等之任一者或二或更多者之有機溶劑;及選自乙纖維素、硝化纖維素、丙烯酸酯系聚合物、甲基丙烯酸酯系聚合物、松脂(rosin)等之任一者或二或更多者之黏結劑樹脂。如果需要,可更包括塑化劑、黏度調節劑、界面活性劑、抗氧化劑、金屬有機化合物等之任一者或二或更多者之混合物。 According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may further include a carrier composed of an organic solvent and an adhesive. In order to mix the conductive composite powder and the second glass component and apply the mixture to screen printing, etc., the mixture is used to form a combination of paste, paint, and ink each having suitable rheology. Can be mixed with general carriers. The carrier is not limited as long as it is a carrier well known in the art. For example, the carrier may be a solution mixed with the following components: terpineol, carbitol, butacarbitol, cyperidine, tetriol, or an ester thereof; any one selected from toluene, xylene, and the like One or two or more organic solvents; and any one or two or more selected from the group consisting of ethyl cellulose, nitrocellulose, acrylate polymers, methacrylate polymers, rosin, etc. Binder resin. If necessary, it may further include any one or a mixture of two or more of a plasticizer, a viscosity modifier, a surfactant, an antioxidant, a metal organic compound, and the like.
此外,載體之混合比例並無限制,只要其係被施用至一般厚膜電阻組合物,且可根據該組合物之施用方法(例如印刷等)所控制即可。 In addition, the mixing ratio of the carrier is not limited, as long as it is applied to a general thick film resistor composition, and can be controlled according to the application method (such as printing) of the composition.
進一步,藉由進一步增加有機溶劑可調整無鉛厚膜電阻組合物之黏度,該有機溶劑可與載體使用的溶劑相同或不同。以100重量份的無鉛厚膜電阻組合物計,可進一步包括10重量份至200重量份的該有機溶劑。更佳地,以100重量份的無鉛厚膜電阻組合物計,可進一步包括30重量份至100重量份的該有機溶劑,但本發明不限於此。 Furthermore, the viscosity of the lead-free thick film resistor composition can be adjusted by further increasing the organic solvent, and the organic solvent can be the same as or different from the solvent used in the carrier. The organic solvent may further include 10 to 200 parts by weight based on 100 parts by weight of the lead-free thick film resistor composition. More preferably, the organic solvent may further include 30 to 100 parts by weight based on 100 parts by weight of the lead-free thick film resistor composition, but the present invention is not limited thereto.
根據本發明之另一例示性實施態樣,提供了一種無鉛厚膜電阻之製造方法,包括:(a)藉由熱處理釕系複合氧化物及第一玻璃成分以製造導電複合粉末;(b)製備包括該導電複合粉末及第二玻璃成分之無鉛厚膜電阻組合物;以及(c)製造藉由燒製該無鉛厚膜電阻組合物以形成之具有一雙重網絡結構之無鉛厚膜電阻,其中第一玻璃成分包括SiO2、B2O3、BaO、及Al2O3,以及第二玻璃成分包括SiO2、B2O3、及Al2O3。 According to another exemplary embodiment of the present invention, a method for manufacturing a lead-free thick film resistor is provided, including: (a) manufacturing a conductive composite powder by heat-treating a ruthenium-based composite oxide and a first glass component; (b) Preparing a lead-free thick film resistor composition including the conductive composite powder and a second glass component; and (c) manufacturing a lead-free thick film resistor having a dual network structure formed by firing the lead-free thick film resistor composition, wherein The first glass component includes SiO 2 , B 2 O 3 , BaO, and Al 2 O 3 , and the second glass component includes SiO 2 , B 2 O 3 , and Al 2 O 3 .
根據本發明之一例示性實施態樣,在步驟(a)中,熱處理之溫度係高於600℃且等於或低於900℃,且該導電複合粉末係藉由該熱處理及接著進行之研磨而製造。較佳地,在步驟(a)中,熱處理之溫度係800℃至900℃,且該導電複合粉末係藉由該熱處理及接著進行之研磨而製造。 According to an exemplary embodiment of the present invention, in step (a), the temperature of the heat treatment is higher than 600 ° C and equal to or lower than 900 ° C, and the conductive composite powder is obtained by the heat treatment and subsequent grinding. Manufacturing. Preferably, in step (a), the temperature of the heat treatment is 800 ° C to 900 ° C, and the conductive composite powder is manufactured by the heat treatment and subsequent grinding.
根據本發明之一例示性實施態樣,導電複合粉末可具有部分結晶結構。由於熱處理,釕系複合氧化物之鈣鈦礦型結晶結構的一部分可與第一玻璃成分反應以分解成釕氧化物,其中在第一玻璃成分中可部分地產生結晶化。因此,能夠藉由釕系複合氧化物及第一玻璃成分形成強的為第一網絡的初級網絡結構。導電複合粉末藉由熱處理可具有為第一網絡的初級網絡結構。由於例如第一玻璃成分之Ba-Si-Al-系結晶的部分結晶化,顯露了玻璃陶瓷行為,從而玻璃軟化點係明顯增加,且第二玻璃成分與釕系複合產物之間的相互反應性被降低。其結果是,藉由熱處理形成的初級網絡結構抑制了在850℃下之膏燒製過程中與第二玻璃成分的反應,此可提供抑制藉由釕系複合氧化物之第二玻璃成分之分解反應的作用。 According to an exemplary embodiment of the present invention, the conductive composite powder may have a partially crystalline structure. Due to the heat treatment, a part of the perovskite-type crystal structure of the ruthenium-based composite oxide may react with the first glass component to be decomposed into a ruthenium oxide, wherein the first glass component may partially crystallize. Therefore, a strong primary network structure that is a first network can be formed by the ruthenium-based composite oxide and the first glass component. The conductive composite powder may have a primary network structure that is a first network by heat treatment. Due to the partial crystallization of, for example, the Ba-Si-Al-based crystals of the first glass component, the glass-ceramic behavior is revealed, and the glass softening point system is significantly increased. Be lowered. As a result, the primary network structure formed by the heat treatment suppresses the reaction with the second glass component during paste firing at 850 ° C, which can suppress the decomposition of the second glass component by the ruthenium-based composite oxide. The role of the reaction.
根據本發明之一例示性實施態樣,在步驟(a)中,該導電複合粉末可包括20重量%至80重量%之釕系複合氧化物及80重量%至20重量%之第一玻璃成分,且更佳地,30重量%至70重量%之釕系複合氧化物及70重量%至30重量%之第一玻璃成分。更佳地,導電複合粉末可藉由熱處理40重量%至60重量%之釕系複合氧化物及60重量%至40重量%之第一玻璃成分而製造。 According to an exemplary embodiment of the present invention, in step (a), the conductive composite powder may include 20% to 80% by weight of a ruthenium-based composite oxide and 80% to 20% by weight of a first glass component. And, more preferably, 30% to 70% by weight of a ruthenium-based composite oxide and 70% to 30% by weight of a first glass component. More preferably, the conductive composite powder can be manufactured by heat-treating 40 to 60% by weight of a ruthenium-based composite oxide and 60 to 40% by weight of a first glass component.
當釕系複合氧化物及第一玻璃成分係包括在上述範圍中時是有效的,因為其容易形成為第一網絡的初級網絡結構,且容易控制溫度特性(TCR)、超載特性(STOL)、及靜電放電特性(ESD)。 It is effective when the ruthenium-based composite oxide and the first glass component system are included in the above range, because it is easy to form a primary network structure of the first network, and it is easy to control temperature characteristics (TCR), overload characteristics (STOL), And electrostatic discharge characteristics (ESD).
此外,當釕系複合氧化物及第一玻璃成分包括在上述範圍中時,可獲得低的電阻值,可防止溫度特性沿(-)方向移動、且(+)之溫度特性不呈現作為導電材料之最佳比電阻之情況,且對維持晶體結構之穩定性係較佳的。 In addition, when the ruthenium-based composite oxide and the first glass component are included in the above range, a low resistance value can be obtained, the temperature characteristics can be prevented from moving in the (-) direction, and the temperature characteristics of (+) are not exhibited as a conductive material. In the case of the best specific resistance, it is better to maintain the stability of the crystal structure.
根據本發明之一例示性實施態樣,導電複合粉末可藉由熱處理及研磨而形成。導電複合粉末的平均顆粒直徑並無限制。舉例而言,當從小顆粒累積至一量時,對應於總量的50%之顆粒直徑D50可為2.0微米或更小。較佳地,D50可為1.0微米至2.0微米。當導電粉末藉由研磨具有上述範圍時是有效的,因為在厚膜電阻組合物中導電粉末可輕易與第二玻璃成分混合,以提供均勻的組合物。 According to an exemplary embodiment of the present invention, the conductive composite powder may be formed by heat treatment and grinding. The average particle diameter of the conductive composite powder is not limited. For example, when accumulated from small particles to an amount, a particle diameter D50 corresponding to 50% of the total amount may be 2.0 micrometers or less. Preferably, D50 can be 1.0 micrometer to 2.0 micrometer. It is effective when the conductive powder has the above range by grinding, because the conductive powder can be easily mixed with the second glass component in the thick film resistance composition to provide a uniform composition.
導電複合粉末可單獨使用作為厚膜電阻組合物,但電性質及流動性可能不足,且稍後待形成之厚膜電阻的平滑度及與基板的黏著力會顯著地降低,因此,較佳將導電複合粉末與第二玻璃成分混合,以形成緻密的次級網絡結構。 The conductive composite powder can be used alone as a thick film resistor composition, but the electrical properties and fluidity may be insufficient, and the smoothness of the thick film resistor to be formed later and the adhesion to the substrate will be significantly reduced. Therefore, it is better to The conductive composite powder is mixed with the second glass component to form a dense secondary network structure.
因此,步驟(b)係將導電複合粉末及第二玻璃成分混合以製備無鉛厚膜電阻組合物的步驟。舉例而言,無鉛厚膜電阻組合物可藉由包括導電複合粉末、載體、及第二玻璃成分所製備,而更佳藉由包括導電複合粉末、載體、第二玻璃成分、導電粉末、及無機顆粒所製備。 Therefore, step (b) is a step of mixing the conductive composite powder and the second glass component to prepare a lead-free thick film resistor composition. For example, a lead-free thick film resistor composition can be prepared by including a conductive composite powder, a carrier, and a second glass component, and more preferably by including a conductive composite powder, a carrier, a second glass component, a conductive powder, and an inorganic material. Granules are prepared.
根據本發明之一例示性實施態樣,無鉛厚膜電阻組合物可包括在10:90至90:10之重量比之導電複合粉末及第二玻璃成分,更佳在20:80至80:20之重量比之導電複合粉末及第二玻璃成分。 According to an exemplary embodiment of the present invention, the lead-free thick film resistor composition may include a conductive composite powder and a second glass component in a weight ratio of 10:90 to 90:10, and more preferably 20:80 to 80:20. Weight ratio of the conductive composite powder and the second glass component.
此外,以上述範圍包括導電複合粉末及第二玻璃成分係較佳的,因為藉由具有上述範圍之無鉛厚膜電阻組合物所製備之無鉛厚膜電阻的電性質可被改善,且可形成均勻的無鉛厚膜電阻。 In addition, it is preferable to include the conductive composite powder and the second glass component in the above range, because the electrical properties of the lead-free thick film resistor prepared by the lead-free thick film resistor composition having the above range can be improved, and uniformity can be formed. Lead-free thick film resistor.
更具體地,在步驟(b)中,無鉛厚膜電阻組合物可藉由包括3重量%至65重量%之導電複合粉末、1重量%至60重量%之第二玻璃成分、0.1重量%至40重量%之導電粉末、及0.1重量%至10重量%之無機顆粒而製備。較佳地,無鉛厚膜電阻組合物可藉由包括25重量%至60重量%之導電複合粉末、20重量%至60重量%之第二玻璃成分、1重量%至20重量%之導電粉末、及0.1重量%至5重量%之無機顆粒而製備,但各個含量係不限於此。 More specifically, in step (b), the lead-free thick film resistor composition may include a conductive composite powder of 3% to 65% by weight, a second glass component of 1% to 60% by weight, and 0.1% to 40% by weight of conductive powder and 0.1% to 10% by weight of inorganic particles. Preferably, the lead-free thick film resistor composition may include a conductive composite powder of 25% to 60% by weight, a second glass component of 20% to 60% by weight, a conductive powder of 1% to 20% by weight, And 0.1% to 5% by weight of inorganic particles, but each content is not limited to this.
當導電複合粉末、第二玻璃成分、導電粉末及無機顆粒包括在上述範圍中時,可容易形成雙重網絡結構,且可容易地控制溫度特性(TCR)、超載特性(STOL)、及靜電放電特性 (ESD),且在製造厚膜電阻時,電阻的平滑度及與基板的黏著力係優異的。 When the conductive composite powder, the second glass component, the conductive powder, and the inorganic particles are included in the above range, a dual network structure can be easily formed, and temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics can be easily controlled. (ESD), and when manufacturing a thick film resistor, the resistance is excellent in smoothness and adhesion to the substrate.
根據本發明之另一例示性實施態樣,提供了一種具有雙重網絡結構的無鉛厚膜電阻,其係藉由將上述之無鉛厚膜電阻組合物網版印刷至一基板上,接著進行燒製而形成。 According to another exemplary embodiment of the present invention, a lead-free thick film resistor having a dual network structure is provided. The lead-free thick film resistor composition is screen-printed onto a substrate and then fired. And formed.
在無鉛厚膜電阻中,電阻值(Rs)可為10歐姆/□至10兆歐姆/□、電阻分佈(CV)可為5%或更低、溫度特性(TCR)可為-100ppm/℃至100ppm/℃、電流雜訊(C-Noise)特性可為12分貝或更低、及在1/8瓦特額定功率下測量之超載特性(STOL)可為0.1%或更低。 In lead-free thick film resistors, the resistance value (Rs) can be 10 ohms / □ to 10 megaohms / □, the resistance distribution (CV) can be 5% or lower, and the temperature characteristic (TCR) can be -100ppm / ℃ to 100ppm / ℃, the current noise (C-Noise) characteristic can be 12 dB or lower, and the overload characteristic (STOL) measured at 1/8 Watt rated power can be 0.1% or lower.
更佳地,在無鉛厚膜電阻中,電阻值(Rs)可為10歐姆/□至500千歐姆/□、電阻分佈(CV)可為5%或更低、溫度特性(TCR)可為-50ppm/℃至50ppm/℃、電流雜訊(C-Noise)特性可為10分貝或更低、及在1/8瓦特額定功率下測量之超載特性(STOL)可為0.05%或更低。 More preferably, in the lead-free thick film resistor, the resistance value (Rs) may be 10 ohms / □ to 500 kohm / □, the resistance distribution (CV) may be 5% or less, and the temperature characteristic (TCR) may be − 50ppm / ℃ to 50ppm / ℃, the current noise (C-Noise) characteristic can be 10dB or lower, and the overload characteristic (STOL) measured at 1/8 Watt rated power can be 0.05% or lower.
為了達到所述物理性質,導電複合粉末較佳可包括30重量%至70重量%之釕系複合氧化物及70重量%至30重量%之第一玻璃成分。更佳地,導電複合粉末可包括40重量%至60重量%之釕系複合氧化物及60重量%至40重量%之第一玻璃成分。 In order to achieve the physical properties, the conductive composite powder may preferably include 30% to 70% by weight of a ruthenium-based composite oxide and 70% to 30% by weight of a first glass component. More preferably, the conductive composite powder may include 40% to 60% by weight of a ruthenium-based composite oxide and 60% to 40% by weight of a first glass component.
根據本發明之另一例示性實施態樣,在網版印刷後,可以將無鉛厚膜電阻乾燥以移除有機溶劑。乾燥可以在100℃至200℃下進行5分鐘至30分鐘,但不限於此。 According to another exemplary embodiment of the present invention, after screen printing, the lead-free thick film resistor can be dried to remove the organic solvent. The drying may be performed at 100 ° C to 200 ° C for 5 minutes to 30 minutes, but is not limited thereto.
如第8圖所示,在根據本發明之一例示性實施態樣之無鉛厚膜電阻中,釕系複合氧化物與第一玻璃成分被熱處理以形成第一網絡,此為初級網絡,然後將第二玻璃成分與其混合並燒製以形成第二網絡,藉此形成雙重網絡,此可於第3圖中證實。 As shown in FIG. 8, in a lead-free thick film resistor according to an exemplary embodiment of the present invention, a ruthenium-based composite oxide and a first glass component are heat-treated to form a first network, which is a primary network. The second glass component is mixed with it and fired to form a second network, thereby forming a dual network, which can be confirmed in Figure 3.
無鉛厚膜電阻即使在雷射修整(laser trimming)、電阻調整等後處理中仍可具有優異的耐久性,且具有優異的電穩定性,因為電阻的電性質(如根據電阻尺寸之電阻(Rs)、TCR等)不會改變。 Lead-free thick film resistors can have excellent durability even in post-processing such as laser trimming and resistance adjustment, and have excellent electrical stability because of the electrical properties of resistors (such as the resistance according to the resistance size (Rs ), TCR, etc.) will not change.
根據本發明之一例示性實施態樣,無鉛厚膜電阻係電子元件,且不僅可施用至單層電路板或多層電路板,也可施用至電極部件(如電容器、電感器等)。 According to an exemplary embodiment of the present invention, the lead-free thick film resistor-based electronic component can be applied not only to a single-layer circuit board or a multilayer circuit board, but also to an electrode component (such as a capacitor, an inductor, etc.).
根據本發明之一例示性實施態樣的晶片電阻包括:第一電極、厚膜電阻、及保護用玻璃,其中厚膜電阻可為藉由將上述之無鉛厚膜電阻組合物網版印刷至一基板上,接著進行燒製而形成之具有雙重網絡結構的無鉛厚膜電阻。 A chip resistor according to an exemplary embodiment of the present invention includes: a first electrode, a thick film resistor, and a protective glass, wherein the thick film resistor may be obtained by screen printing the lead-free thick film resistor composition described above to a On the substrate, a lead-free thick film resistor with a dual network structure is formed by firing.
作為一具體實例,本發明之無鉛厚膜電阻可被包括在如第2圖示出之晶片電阻中。該晶片電阻可包括:第一電極、厚膜電阻、及保護用玻璃。 As a specific example, the lead-free thick film resistor of the present invention may be included in a chip resistor as shown in FIG. 2. The chip resistor may include a first electrode, a thick film resistor, and a protective glass.
第一電極不包括鉛,且無機黏著劑之成分可根據電阻之規格控制,以不被電性質(如溫度特性及電阻特性等)所影響。 The first electrode does not include lead, and the composition of the inorganic adhesive can be controlled according to the specifications of the resistance so as not to be affected by the electrical properties (such as temperature characteristics and resistance characteristics).
無機黏著劑較佳不包括鉛作為玻璃成分,較佳具有 500℃至700℃之軟化點,且較佳更包括具有控制溫度特性功能之如TiO2、MnO2、Nb2O5等無機顆粒。 The inorganic adhesive preferably does not include lead as a glass component, preferably has a softening point of 500 ° C to 700 ° C, and more preferably includes inorganic particles such as TiO 2 , MnO 2 , Nb 2 O 5 and the like having functions of controlling temperature.
進一步,較佳將保護用玻璃施用至電阻,以改善在雷射修整、電阻調整等後處理中之穩定性。 Further, it is preferable to apply protective glass to the resistor to improve the stability in post-processing such as laser trimming and resistance adjustment.
保護用玻璃不包括鉛,且具有500℃至600℃之軟化點,且可更包括在第一電極中不可用的B2O3成分。當保護用玻璃之軟化點具有上述範圍時是較佳的,因為與無鉛厚膜電阻之緊密黏著力係優異的,且在約500℃之燒製溫度下的電阻值改變係小的。 The protective glass does not include lead, has a softening point of 500 ° C. to 600 ° C., and may further include a B 2 O 3 component that is not available in the first electrode. When the softening point of the protective glass has the above range, it is preferable because the adhesion to the lead-free thick film resistor is excellent, and the resistance value change at a firing temperature of about 500 ° C is small.
在下文中,將詳細描述關於無鉛厚膜電阻組合物、無鉛厚膜電阻、及其製造方法之較佳例示性實施態樣及測量物理性質之方法。 Hereinafter, a preferred exemplary embodiment of a lead-free thick film resistor composition, a lead-free thick film resistor, and a manufacturing method thereof and a method of measuring physical properties will be described in detail.
物理性質之測量Measurement of physical properties
1.變異係數(CV)之評估1. Evaluation of the coefficient of variation (CV)
根據本發明之無鉛厚膜電阻組合物係經印刷、接著燒製在電極上以製造20個電阻,而各電阻之電阻值係藉由多用電表(multimeter)所測量。計算這些電阻值之平均值及標準差,並且將電阻值之標準差除以平均值以推導出電阻分佈(CV),且電阻分佈係以百分比表示。 The lead-free thick film resistor composition according to the present invention is printed and then fired on an electrode to make 20 resistors, and the resistance value of each resistor is measured by a multimeter. Calculate the average and standard deviation of these resistance values, and divide the standard deviation of the resistance values by the average to derive the resistance distribution (CV), and the resistance distribution is expressed as a percentage.
2.電阻之溫度係數(TCR)之評估2. Evaluation of temperature coefficient of resistance (TCR)
TCR之評估係藉由確認以室溫(25℃)為基礎將溫度升至125℃時電阻值的變化率而進行。具體而言,當在25℃及 125℃下各別電阻值以R25(Ω/□)及R125(Ω/□)代表,且TCR係藉由以下方程式所推導,其係以ppm/℃表示,且結果顯示於表4。 The TCR was evaluated by confirming the rate of change in resistance value when the temperature was raised to 125 ° C based on room temperature (25 ° C). Specifically, when the respective resistance values at 25 ° C and 125 ° C are represented by R 25 (Ω / □) and R 125 (Ω / □), and TCR is derived by the following equation, it is expressed in ppm / ℃ The results are shown in Table 4.
[方程式]TCR=(R125-R25)/R25/100×1000000 [Equation] TCR = (R 125 -R 25 ) / R 25/100 × 1000000
3.短時超載特性(STOL)之評估3. Evaluation of short-term overload characteristics (STOL)
將無鉛厚膜電阻在測試電壓施用於其上5秒後放置30分鐘,並確認電壓施用前後的電阻值改變率。測試電壓係額定電壓的2.5倍。額定電壓為,其中R為電阻值(Ω/□)。此外,對於具有超過200V電阻值之計算測試電壓的電阻,測試電壓為200V,結果顯示於表4。 The lead-free thick-film resistor was left for 30 minutes 5 seconds after the test voltage was applied thereto, and the resistance value change rate before and after the voltage application was confirmed. The test voltage is 2.5 times the rated voltage. Rated voltage is , Where R is the resistance value (Ω / □). In addition, for a resistor having a calculated test voltage exceeding 200 V, the test voltage is 200 V, and the results are shown in Table 4.
4.電流雜訊(C-Noise)之評估4. Evaluation of C-Noise
經燒製之無鉛厚膜電阻係被安置(mounted)在電流雜訊測試機中,且測量所顯示之的電阻值及此時的雜訊值,結果顯示於表4。 The fired lead-free thick film resistor was mounted in a current noise tester, and the resistance value displayed and the noise value at this time were measured. The results are shown in Table 4.
5.靜電放電特性(ESD)之評估5. Evaluation of electrostatic discharge characteristics (ESD)
使用靜電放電測試儀(ELECTRO STATIC DISCHARGE SIMULATOR ESS-066),將1kV之電壓以數個奈秒的速度以1秒開及1秒關的方式在經燒製之無鉛厚膜電阻上施用5次。計算在1kV之電壓施用前後間之電阻值變化,結果顯示於表4。 Using an electrostatic discharge tester (ELECTRO STATIC DISCHARGE SIMULATOR ESS-066), a voltage of 1 kV was applied to the fired lead-free thick film resistor 5 times at a speed of several nanoseconds with a speed of 1 second on and 1 second off. The change in resistance between before and after the application of a voltage of 1 kV was calculated. The results are shown in Table 4.
6.透過XRD之晶體結構之確認6. Confirmation of crystal structure through XRD
將經乾燥及經燒製之無鉛厚膜電阻水平地放置在XRD測量儀中之樣品板上,接著,測量10℃至80℃的2θ值。其結果顯示於第4圖至第6圖。 The dried and fired lead-free thick film resistor was horizontally placed on a sample plate in an XRD measuring instrument, and then a 2θ value of 10 ° C to 80 ° C was measured. The results are shown in FIGS. 4 to 6.
[實施例1至24以及比較實施例1至9] [Examples 1 to 24 and Comparative Examples 1 to 9]
導電複合粉末之製備Preparation of conductive composite powder
根據下方表2中顯示之組合物含量(公克)來稱重各成分,該等成分包括下方表1所示之第一玻璃成分及第二玻璃成分,且藉由球磨機(ball mill)混合2小時。此外,將混合物在800℃下熱處理30分鐘以獲得燒結體。將獲得的燒結體藉由研磨機研磨12小時。最終粉末具有1.5微米之平均顆粒尺寸,測量XRD以確認晶體結構。 Weigh each component according to the composition content (g) shown in Table 2 below, which includes the first glass component and the second glass component shown in Table 1 below, and mix by a ball mill for 2 hours . Further, the mixture was heat-treated at 800 ° C for 30 minutes to obtain a sintered body. The obtained sintered body was ground by a grinder for 12 hours. The final powder had an average particle size of 1.5 microns, and XRD was measured to confirm the crystal structure.
無鉛厚膜電阻組合物之製備Preparation of lead-free thick film resistor composition
使用具有顯示於下方表3之組合物含量(公克)之無鉛厚膜電阻組合物,使用由12重量%之作為有機黏著劑之乙基纖維素樹脂及88重量%之其中以重量比3:16混合之丁卡必醇乙酸酯(BCA)及萜品醇(TPNL)之有機溶劑所組成的有機載體,以及使用分散劑(BYK-111)作為添加劑。使用P/L混合器將組合物攪拌2小時,接著使用三滾筒磨機(3-roll mill),藉由5次釋放(release)及5次壓縮(compression)的方式來進行分散。將獲得之膏在65℃下熟化(aging)24小時,並以有機溶劑(即,萜品醇(TPNL))控制黏度,且接著進行過濾程序。 A lead-free thick film resistor composition having a composition content (g) shown in Table 3 below was used, and 12% by weight of an ethyl cellulose resin as an organic adhesive and 88% by weight of which was in a weight ratio of 3:16 An organic vehicle composed of a mixed organic solvent of tetracarbitol acetate (BCA) and terpineol (TPNL), and a dispersant (BYK-111) is used as an additive. The composition was stirred for 2 hours using a P / L mixer, and then dispersed using a 3-roll mill with 5 releases and 5 compressions. The obtained paste was aged at 65 ° C. for 24 hours, and the viscosity was controlled with an organic solvent (ie, terpineol (TPNL)), and then a filtration procedure was performed.
無鉛厚膜電阻之製造Manufacturing of lead-free thick film resistors
將Ag-Pd導體膏以U型(U-patterns)網版印刷至96%純氧化鋁基板,且在150℃下乾燥10分鐘。Ag的含量為95重量%且Pd的含量為5重量%。經乾燥的樣品在850℃下燒製10分鐘。將實施例之無鉛厚膜電阻組合物在形成導體之氧化鋁基板上網版印刷成1毫米×1毫米之預定形狀,接著在150℃下乾燥10分鐘,且在850℃下燒製10分鐘,以獲得無鉛厚膜電阻。該無鉛厚膜電阻具有8.5微米之厚度,且其物理性質係經測量並顯示於下方表4。 The Ag-Pd conductor paste was printed on a U-patterns screen to a 96% pure alumina substrate, and dried at 150 ° C. for 10 minutes. The content of Ag is 95% by weight and the content of Pd is 5% by weight. The dried sample was fired at 850 ° C for 10 minutes. The lead-free thick-film resistor composition of the example was printed on a screen of a conductor forming an alumina substrate into a predetermined shape of 1 mm × 1 mm, followed by drying at 150 ° C. for 10 minutes, and firing at 850 ° C. for 10 minutes. Obtain lead-free thick film resistors. The lead-free thick film resistor has a thickness of 8.5 microns, and its physical properties are measured and shown in Table 4 below.
第3圖顯示根據本發明之一例示性實施態樣之無鉛厚膜電阻之表面及橫截面的掃描式電子顯微鏡(SEM)影像。參考第3圖,可確認雙重網絡結構被均勻地形成。 FIG. 3 shows a scanning electron microscope (SEM) image of a surface and a cross section of a lead-free thick film resistor according to an exemplary embodiment of the present invention. Referring to FIG. 3, it can be confirmed that the dual network structure is uniformly formed.
此外,第4圖、第5圖及第6圖係根據本發明之一例示性實施態樣及比較實施例之導電複合粉末的XRD測量圖。 In addition, FIG. 4, FIG. 5, and FIG. 6 are XRD measurement diagrams of the conductive composite powder according to an exemplary embodiment of the present invention and a comparative example.
第4圖顯示具有表2之組合物3之導電複合粉末在根據650℃至900℃之熱處理溫度範圍之熱處理後的XRD測量圖;且第5圖及第6圖顯示具有表2之導電複合粉末5及13的XRD測量圖。 FIG. 4 shows the XRD measurement chart of the conductive composite powder having the composition 3 of Table 2 after heat treatment according to the heat treatment temperature range of 650 ° C. to 900 ° C .; and FIG. 5 and FIG. 6 show the conductive composite powder having Table 2 XRD measurement chart of 5 and 13.
如第4圖所示,可以瞭解,藉由在具有30°之2θ值之熱處理,即使該熱處理係以高於600℃的溫度進行,本發明之導電複合粉末仍具有穩定的晶體結構。此外,如第5圖及第6圖所示,可確認該導電複合粉末5及13藉由熱處理也顯現穩定的晶體結構。 As shown in FIG. 4, it can be understood that by conducting a heat treatment with a 2θ value of 30 °, the conductive composite powder of the present invention has a stable crystal structure even if the heat treatment is performed at a temperature higher than 600 ° C. In addition, as shown in FIGS. 5 and 6, it was confirmed that the conductive composite powders 5 and 13 also exhibit a stable crystal structure by heat treatment.
第7圖顯示將膏在150℃乾燥10分鐘所獲得之塗覆膜之XRD圖,以及在850℃燒製10分鐘所獲得之塗覆膜之XRD圖,其中該膏藉由將導電複合粉末及第二玻璃成分混合所製得。 Figure 7 shows the XRD pattern of the coating film obtained by drying the paste at 150 ° C for 10 minutes, and the XRD pattern of the coating film obtained by firing at 850 ° C for 10 minutes. The second glass component is prepared by mixing.
如第6圖所示,可以瞭解,只有在施用本發明之導電複合粉末時,才顯示穩定的晶體結構。 As shown in Fig. 6, it can be understood that only when the conductive composite powder of the present invention is applied, it shows a stable crystal structure.
此外,當不包括既有的導電複合粉末時,燒製後的晶體結構改變係大的。相反地,可以瞭解,當包括根據本發明之導電複合粉末時,與經乾燥之塗覆膜相比,能夠在燒製後形成穩定的雙重網絡結構且沒有太大的晶體結構改變。 In addition, when the existing conductive composite powder is not included, the crystal structure change after firing is large. On the contrary, it can be understood that when the conductive composite powder according to the present invention is included, compared with the dried coating film, a stable double network structure can be formed after firing without much change in crystal structure.
進一步,可以瞭解,當釕系複合氧化物(CaxSryBaz)RuO3,使用於根據本發明的導電複合粉末時,在燒製後雙重網絡結構均勻形成且沒有太大的晶體結構改變,其中,在(CaxSryBaz)RuO3中,需滿足x+y+z=1、0x<1、0y<1、0z<1、以及0<x+y1。此外,以如此製備的無鉛厚膜電阻組合物形成的無鉛厚膜電阻也顯現優異的溫度特性(TCR)、超載特性(STOL)、及靜電放電特性(ESD)。具體而言,係使用在CaxSryRuO3中滿足x=54或80、y=46或20、及z=0的釕系複合氧化物。 Further, it can be understood that when a ruthenium-based composite oxide (Ca x Sr y Ba z ) RuO 3 is used in the conductive composite powder according to the present invention, the double network structure is uniformly formed after firing without much change in crystal structure. , Where (Ca x Sr y Ba z ) RuO 3 needs to satisfy x + y + z = 1, 0 x <1, 0 y <1, 0 z <1, and 0 <x + y 1. In addition, the lead-free thick film resistor formed with the lead-free thick film resistor composition thus prepared also exhibits excellent temperature characteristics (TCR), overload characteristics (STOL), and electrostatic discharge characteristics (ESD). Specifically, a ruthenium-based composite oxide that satisfies x = 54 or 80, y = 46 or 20, and z = 0 in Ca x Sr y RuO 3 is used.
如上所述,儘管描述了本發明的較佳實施態樣,但本發明應當被解釋為包括所有的變化、修飾、及均等物,使得本發明可以藉由適當地修改上述例示性實施態樣而均等地被利用。因此,前文描述並非意欲限制由以下申請專利範圍之限制條件所定義的本發明範圍。 As described above, although the preferred embodiments of the present invention have been described, the present invention should be construed to include all changes, modifications, and equivalents, so that the present invention can be modified by appropriately modifying the above-mentioned exemplary embodiments. Equally utilized. Therefore, the foregoing description is not intended to limit the scope of the invention, which is defined by the following limitations of the scope of the patent application.
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