TWI723424B - 半導體裝置之製造方法 - Google Patents

半導體裝置之製造方法 Download PDF

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TWI723424B
TWI723424B TW108120656A TW108120656A TWI723424B TW I723424 B TWI723424 B TW I723424B TW 108120656 A TW108120656 A TW 108120656A TW 108120656 A TW108120656 A TW 108120656A TW I723424 B TWI723424 B TW I723424B
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carboxylic acid
concentration
gas
acid gas
furnace
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TW108120656A
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TW202036822A (zh
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宮崎力
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日商東芝記憶體股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/008—Soldering within a furnace
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

本發明係關於一種半導體裝置之製造方法。 根據一實施形態，將第1半導體元件之焊料凸塊與第2半導體元件之第2凸塊電極暫時固定而形成積層體。其次，一面將爐內設為羧酸之還原溫度以上且未達焊料凸塊之熔融溫度之溫度，一面將爐內設為第1羧酸氣體濃度。然後，一面將爐內之溫度升溫至熔融溫度為止，一面將爐內設為第2羧酸氣體濃度。接著，將爐內之溫度維持為熔融溫度以上之溫度，使焊料凸塊熔融。第2羧酸氣體濃度係低於第1羧酸氣體濃度，且係包含能夠將焊料凸塊之氧化膜還原之最低限度的羧酸氣體之濃度。當爐內之溫度達到熔融溫度時，至少爐內具有第2羧酸氣體濃度。

Description

半導體裝置之製造方法
此處說明之多種實施形態均係關於半導體裝置之製造方法。
已知有一種半導體裝置，積層複數個半導體晶片，利用凸塊將積層之半導體晶片之凸塊電極間電性連接。凸塊理想為具有穩定之連接形狀，且凸塊與凸塊電極之間之接觸界面之氧化膜被除去。
本發明之一實施形態提供一種半導體裝置之製造方法，於積層之半導體元件之凸塊電極間具有穩定之連接形狀，且能夠除去與凸塊電極之接觸界面之氧化膜。
根據本發明之一實施形態，半導體裝置之製造方法包含積層體形成工序、排氣工序、氧化膜除去工序、還原性氣體濃度降低工序、及熔融工序。於上述積層體形成工序中，將具有第1凸塊電極及配置於上述第1凸塊電極上之焊料凸塊之第1半導體元件、具有第2凸塊電極之第2半導體元件，藉由暫時固定上述焊料凸塊與上述第2凸塊電極而積層，從而形成積層體。於上述排氣工序中，將配置有上述積層體之爐內排氣。於上述氧化膜除去工序中，一面將上述爐內之溫度設為顯現羧酸還原作用之還原溫度以上且未達上述焊料凸塊熔融之熔融溫度之溫度，一面以上述爐內變成第1羧酸氣體濃度之方式，向上述爐內導入包含羧酸氣體與惰性氣體之還原性氣體，將上述焊料凸塊表面之氧化膜除去。於上述還原性氣體濃度降低工序中，一面將上述爐內之溫度升溫至上述熔融溫度為止，一面將上述爐內之羧酸氣體之濃度降低至第2羧酸氣體濃度為止。於上述熔融工序中，將上述爐內之溫度維持為上述熔融溫度以上之溫度，使上述焊料凸塊熔融，從而將上述焊料凸塊與上述第2凸塊電極連接。上述第2羧酸氣體濃度係低於上述第1羧酸氣體濃度，且包含能夠使咬入上述焊料凸塊與上述第2凸塊電極之間之上述焊料凸塊之氧化膜還原之最低限度的羧酸氣體之濃度。於上述熔融工序之開始時間點，至少上述爐內具有上述第2羧酸氣體濃度。
根據上述構成，可提供一種半導體裝置之製造方法，於積層之半導體元件之凸塊電極間具有穩定之連接形狀，且能夠將與凸塊電極之接觸界面之氧化膜除去。
以下參照圖式詳細地說明實施形態之半導體裝置之製造方法。再者，本發明並非由該等實施形態限定。於圖式中，相同符號表示相同或相似部分。又，以下實施形態中使用之半導體裝置之剖視圖係模式圖，層之厚度與寬度之關係、各層之厚度之比率等有時與實物並不相同。
(第1實施形態)圖1係表示第1實施形態之半導體裝置之製造方法之順序之一例的剖視圖。圖2係模式性表示第1實施形態之半導體裝置之製造方法之焊料凸塊附近之狀況的剖視圖。圖3係模式性表示焊料凸塊連接時之狀況之圖。圖2及圖3中，表示將半導體晶片10與半導體晶片20-1之間之凸塊電極11、21間放大後之圖。
如圖1(a)所示，於半導體裝置之製造中，要準備複數個半導體元件即半導體晶片10、20-1～20-N(N為任意之自然數)。此處，準備半導體晶片10、及複數個半導體晶片20-1～20-N(再者，以下不需要區分各個半導體晶片20-1～20-N時，表述為半導體晶片20)。半導體晶片10於作為其中一面之上表面具有凸塊電極11。半導體晶片20於作為其中一面之下表面具有凸塊電極21、及連接於凸塊電極21上之焊料凸塊22，於作為另一面之上表面具有凸塊電極23。
各凸塊電極11、21、23係成為將2個半導體晶片10、20間電性連接及機械連接之連接部之電極。凸塊電極11於半導體晶片10之上表面之特定區域內排列成例如矩陣狀。凸塊電極21、23分別於半導體晶片20之下表面及上表面之特定區域內排列成例如矩陣狀。本例中，各凸塊電極11、21、23具有平坦之焊墊形狀。各凸塊電極包含使用Cu、Au、Ni、Pd等金屬單體之金屬膜或將該等金屬積層多層而成之複合膜、或者該等金屬之合金膜。
如圖2(a)所示，於各凸塊電極11、21、23之側面，存在凸塊電極11、21、23之表面被氧化之氧化膜31。凸塊電極11、21之側面存在之氧化膜31具有如下功能：於焊料凸塊22之熔融時，使熔融之焊料不向凸塊電極11、21之側面潤濕擴散。若凸塊電極11、21、23之側面不存在氧化膜31，則如圖3所示，於焊料凸塊22熔融時，熔融之焊料會向凸塊電極11、21之側面潤濕擴散。即，焊料向凸塊電極11、21之側面流回，結果得到之焊料凸塊22具有於高度方向之中央附近凹陷之形狀。又，如此向凸塊電極11、21之側面流回之焊料21a有可能與於平行於凸塊電極11、21之配置面之方向鄰接之凸塊電極11、21或焊料凸塊22短路。因此，熔融焊料凸塊22時，需要使凸塊電極11、21、23之側面之氧化膜31不被除去。
焊料凸塊22於半導體晶片20之下表面之凸塊電極21上與凸塊電極21同樣地配置成例如矩陣狀。焊料凸塊22例如以鍍覆法形成、或者使用由焊料合金形成之微小球形成。焊料凸塊22包含例如Sn、Ag、Cu、Au、Bi、Zn、In等單體金屬或該等金屬之複合物、或者該等金屬之合金。剛形成於凸塊電極21上之後之焊料凸塊22之表面並不存在氧化膜，但隨著時間經過，如圖2(a)所示，焊料凸塊22之表面氧化，形成氧化膜32。形成於焊料凸塊22之表面之氧化膜32於連接焊料凸塊22與凸塊電極11、23時成為焊料凸塊22與凸塊電極11、23之間之電阻增大、或者焊料凸塊22與凸塊電極11、23之間發生連接不良之主要原因。因此，要求於熔融焊料凸塊22之前，儘可能地除去焊料凸塊22之表面之氧化膜32。
半導體晶片10及半導體晶片20例如係矽(Si)晶片等，但亦可至少一方為Si插入式基板。即，第1半導體元件與第2半導體元件之組合並無特別限定，除了半導體晶片10與半導體晶片20之組合以外，還有Si插入式基板與半導體晶片10、20之組合、半導體晶片10、20與Si插入式基板之組合等。
其次，如圖1(b)所示，於支持基板40上搭載半導體晶片10。然後，以半導體晶片10之凸塊電極11與半導體晶片20-1之焊料凸塊22重疊之方式進行對準後，於半導體晶片10上積層半導體晶片20。此時，將凸塊電極11與焊料凸塊22暫時固定。暫時固定只要能獲得於下一工序中實施氧化膜除去時上下半導體晶片10、20-1不脫離之強度即可。凸塊電極11與焊料凸塊22之暫時固定有以下等方法：一面使用脈衝加熱器加熱型接合機加熱至未達焊料凸塊22之熔點一面施加荷重而進行固定；或者並用感光性接著劑或非導電性接著劑作為未圖示之固定材料。再者，支持基板40例如係引線框架或玻璃環氧基板。
然後，將半導體晶片20-2之焊料凸塊22、與和半導體晶片10暫時固定之半導體晶片20之凸塊電極23以相同方法暫時固定。直至半導體晶片20-N暫時固定為止反覆進行該動作。藉此，獲得暫時固定有半導體晶片10～20-N之積層體50。
其次，對圖1(b)中暫時固定之積層體50進行還原回焊處理，將焊料凸塊22與凸塊電極11、23正式接合。上下鄰接之半導體晶片10、20之凸塊電極11、23與焊料凸塊22之間之暫時固定係於焊料凸塊22之表面存在氧化膜32之狀態下實施，因此凸塊電極11、23與焊料凸塊22之接觸界面處於咬入有氧化膜32之狀態。但，如圖2(b)所示，凸塊電極11與焊料凸塊22為暫時固定之狀態，因此凸塊電極11與焊料凸塊22之接觸界面存在間隙G。因此，使羧酸氣體接觸焊料凸塊22之表面存在之氧化膜32而將其除去後，熔融焊料凸塊22，本實施形態中進行還原回焊處理，於存在羧酸氣體之氣氛下進行該熔融，熔融焊料凸塊22時將咬入接觸界面之氧化膜32除去。以下，說明該還原回焊處理。
圖4係模式性表示還原回焊處理裝置之構成之一例之圖。還原回焊處理裝置100具有加熱爐110、排氣處理部130、氣體導入部150。加熱爐110具有可密閉之結構。加熱爐110於內部具有保持加工對象且具有加熱機構之載物台111。載物台111上可載置例如配置有複數個暫時固定之積層體50之搬送板60。
排氣處理部130具備：真空泵132，其經由配管131而與加熱爐110連接，向外部排出加熱爐110內之氣體；排氣閥133，其切換真空泵132之排氣接通與斷開；及除外裝置134，其經由配管131而與真空泵132連接，使藉由真空泵132排氣之氣體無害化。
氣體導入部150具備：惰性氣體貯存部152，其經由配管151而與加熱爐110連接，貯存惰性氣體；及閥153，其切換惰性氣體向加熱爐110之供給之接通與斷開。惰性氣體貯存部152中貯存氮氣等惰性氣體。藉由該配管151連接之路徑，係用於大氣開放之情形，即，使處於內部被排氣後之狀態之加熱爐110恢復成大氣壓。
又，氣體導入部150具備惰性氣體貯存部155、還原氣體生成部156。惰性氣體貯存部155中貯存作為產生羧酸氣體時使用之載氣使用、且作為調整羧酸氣體之濃度之稀釋氣體使用之惰性氣體。作為惰性氣體可使用氮氣、He氣體、Ne氣體、Ar氣體、Kr氣體、Xe氣體等惰性氣體。圖中，分開地設置有惰性氣體貯存部152及惰性氣體貯存部155，但用於大氣開放之惰性氣體、與用於還原性氣體生成之惰性氣體使用相同氣體之情形時，亦可將惰性氣體貯存部共通化。
連接於惰性氣體貯存部155之配管161，於中途被分支為稀釋氣體配管162與載氣配管163。稀釋氣體配管162連接於加熱爐110。稀釋氣體配管162中設置有氣體流量控制器157，該氣體流量控制器157控制作為導入加熱爐110內之稀釋氣體之惰性氣體之流量。載氣配管163設置有氣體流量控制器158，該氣體流量控制器158控制作為導入還原氣體生成部156之載氣之惰性氣體之流量。作為氣體流量控制器157、158可使用質量流量控制器等。載氣配管163連接於還原氣體生成部156。又，配管161中設置有切換惰性氣體之供給之接通與斷開之閥165。
還原氣體生成部156係收容有羧酸液體1562之密閉容器1561。密閉容器1561連接有載氣配管163、及混合氣體配管164，該混合氣體配管164將包含密閉容器1561內生成之羧酸蒸汽與載氣之混合氣體導入加熱爐110內。載氣配管163之前端配置於羧酸液體1562中。又，混合氣體配管164之一端以不接觸羧酸液體1562之方式設置於密閉容器1561，另一端連接稀釋氣體配管162。羧酸液體1562於羧酸自身為液體時可為液體，亦可為按特定濃度含有羧酸之羧酸水溶液。還原氣體生成部156具有加熱羧酸液體1562之加熱部1563。加熱部1563例如加熱密閉容器1561。藉由加熱密閉容器1561，於密閉容器1561內產生羧酸蒸汽。混合氣體配管164中之混合氣體與稀釋氣體配管162中之稀釋氣體混合，變成含有特定濃度之羧酸氣體之還原性氣體，並被供給至加熱爐110內。
羧酸氣體用於將焊料凸塊22之表面存在之氧化膜32還原而除去。作為氧化膜32之還原劑使用之羧酸並無特別限定，例如列舉甲酸、乙酸、丙烯酸、丙酸、草酸、琥珀酸、丙二酸等脂肪族之一元或二元之低級羧酸。該等之中，較佳使用甲酸，其自身成本及用於氣體化之成本低，且氧化膜32之還原作用優異。再者，以下以使用甲酸作為羧酸之代表例之情形為中心進行說明，但作為氧化膜32之還原劑之羧酸並不限定於此。又，還原氣體生成部156之構成係使用起泡方式時之一例，只要能夠將羧酸蒸汽供給至加熱爐110內，則亦可使用烘烤方式、直接氣化方式等其他構成。
此處，對圖4所示之還原回焊處理裝置100之第1實施形態之還原回焊處理進行說明。圖5係表示第1實施形態之還原回焊處理之條件之一例之圖。該圖中橫軸表示時間，左側之縱軸表示溫度，右側之縱軸表示加熱爐110內之壓力及羧酸氣體之濃度(體積%)。
首先，將搭載於支持基板40之複數個暫時固定之積層體50配置於搬送板60，並載置於加熱爐110(回焊爐)內之載物台111上。然後，為了使加熱爐110內變成減壓氣氛，實施利用真空泵132將加熱爐110內排氣之排氣處理(步驟S11)。加熱時殘留於加熱爐110內之氧使焊料凸塊22氧化，因此較佳於自大氣壓狀態(1.01×105 Pa)起1×103 Pa以下、更理想為5Pa左右之減壓狀態下將加熱爐110內排氣。
進行還原處理，向這種減壓氣氛之加熱爐110內導入作為還原性氣體之羧酸氣體，使焊料凸塊22之氧化膜還原(步驟S12)。該還原處理中，以加熱爐110內之溫度為顯現羧酸氣體之還原作用之還原溫度T1以上、且未達焊料凸塊22之熔點T2之溫度範圍之方式，利用載物台111之加熱機構進行加熱。又，加熱爐110內之壓力被維持為特定值，羧酸濃度亦被維持為特定值C1。以下，具體地說明該還原處理。
如圖4所示，利用加熱部1563加熱還原氣體生成部156之密閉容器1561收容之羧酸水溶液，使密閉容器1561內產生羧酸蒸汽。藉由自載氣配管163向該狀態之密閉容器1561內流入載氣，而自混合氣體配管164送出由載氣與羧酸蒸汽混合而成之混合氣體。作為載氣使用氮氣、He氣體、Ne氣體、Ar氣體、Kr氣體、Xe氣體等。
由於混合氣體配管164連接稀釋氣體配管162，因此混合氣體與稀釋氣體合流。於稀釋氣體配管162內流動之惰性氣體、混合氣體混合而生成羧酸氣體濃度得到調整之還原性氣體，還原性氣體被導入加熱爐110內。稀釋氣體係用於調整羧酸氣體之濃度之氣體。稀釋氣體配管162中，為了變成還原加熱爐110內之焊料凸塊22上存在之氧化膜所需之羧酸之濃度，利用氣體流量控制器157調整稀釋氣體之流量，利用氣體流量控制器158構成載氣之流量。與載氣同樣地，稀釋氣體使用惰性氣體。作為稀釋氣體可使用氮氣等，但亦可使用與載氣相同之氣體。
再者，預先藉由實驗求出加熱爐110內具有特定壓力時之加熱爐110內之羧酸氣體之濃度、氣體流量控制器157、158之惰性氣體之流量、排氣閥133之開度之間之關聯信息。然後，向加熱爐110內導入還原性氣體時，按照該關聯信息進行氣體流量控制器157、158之惰性氣體之流量控制，且利用排氣閥133之動作調整加熱爐110內之壓力，由此控制加熱爐110內之羧酸氣體之濃度。
即，一直向加熱爐110內供給新之還原性氣體。又，加熱爐110之氣氛壓較佳設定為較大氣壓低之狀態、例如維持於1.3～8×104 Pa之範圍內。若加熱爐110內之壓力過低則有可能因真空隔熱引起之加熱不足導致焊料凸塊22未熔融，處於大氣壓附近時會導致包含羧酸氣體之外部氣體被捲入焊料而引起空隙不良。藉此，利用還原性氣體還原氧化膜32時產生之氣體不會滯留，可向周圍釋放，從而抑制還原時產生之氣體進入焊料凸塊22與凸塊電極11、23之接合體(連接體)25內之情形。具體之氣氛壓依賴於羧酸氣體之導入量，但理想的是例如2.7×104 Pa以下。
於1.3×104 Pa以上且8×104 Pa以下之減壓氣氛下，若存在特定存在量(濃度)之羧酸氣體，就能將焊料凸塊22之表面之氧化膜32還原除去。例如，當加熱爐110內之壓力為2.7×104 Pa之情形時，較佳以羧酸氣體濃度為0.6體積%～9.2體積%之範圍之方式導入還原性氣體。若將該羧酸氣體濃度換算為例如甲酸之莫耳濃度則為3.19×10-6 mol/L～2.87×10-3 mol/L之範圍。
若還原處理工序中加熱爐110內之羧酸氣體之濃度過高，則多餘之羧酸氣體有可能會進入熔融之焊料凸塊22內成為空隙。另一方面，若羧酸氣體之濃度過低，則無法充分獲得利用羧酸氣體之氧化膜32之還原作用，有可能導致焊料凸塊22之連接不良及電阻值增大等。因此，理想的是上述羧酸氣體濃度之範圍。
於上述環境下向加熱爐110內導入還原性氣體後，或者於導入還原性氣體之大致同時，利用載物台111之加熱機構以特定升溫速度(例如20～50℃/分)使加熱爐110內升溫。此時，將加熱爐110內之溫度控制為顯現羧酸之還原作用之還原溫度T1以上、且未達焊料凸塊22之熔點T2之溫度。
使用甲酸作為羧酸之情形時，於150℃以上之溫度顯現氧化膜32之還原作用。即，甲酸對氧化膜32之還原溫度T1約為150℃，若變成150℃以上之溫度則氧化膜32還原而被除去。如此之氧化膜32之還原溫度T1以上之溫度區域，將焊料凸塊22於甲酸氣體中暴露例如數分鐘，由此可將焊料凸塊22之表面存在之氧化膜還原而除去。
但，構成暫時固定之積層體50之各半導體晶片20上配置之焊料凸塊22之數量伴隨著凸塊尺寸微小化或凸塊間距微細化等而超過1000個。還原回焊處理之對象係此種具有複數個焊料凸塊22之半導體晶片20積層而成之積層體50，且加熱爐110內成批地對複數個積層體50進行還原回焊處理，因此焊料凸塊22之數量有時超過800,000個。還原開始前該等焊料凸塊22之氧化膜32之狀態並不相同，因此要將所有焊料凸塊22之氧化膜同樣地除去，需要足夠長之還原處理之時間。
另一方面，若凸塊連接所需之焊料凸塊22之接合體25以外之凸塊電極11、21、23之側面之氧化膜31被還原，則如圖3所示焊料凸塊22之焊料向凸塊電極11、21、23之側面潤濕擴散，導致接合體25之連接所需之焊料之體積減少。又，減少還原力而以一定之濃度抑制向凸塊電極11、21、23之側面潤濕擴散之方法，使焊料凸塊22之還原時間變長，預計會因熱歷程引起焊料凸塊22之連接弊端。該方法中例如以低溫進行金屬之固相擴散，先形成高熔點之金屬化合物，會阻礙焊料凸塊22於熔點T2之熔融。
因此，第1實施形態中，對還原處理後之處理下了功夫，以便於還原處理後，能夠不使凸塊電極11、21、23之側面之氧化膜31還原，而將焊料凸塊22與凸塊電極11、23之間未還原而殘留之氧化膜32除去。即，於還原處理後之焊料凸塊22之熔融處理時，亦以加熱爐110內存在還原性氣體之方式控制加熱爐110內之氣體環境。
於步驟S12之還原處理工序後，實施升溫處理，使加熱爐110之溫度升溫至焊料凸塊22之熔點(熔融溫度)T2以上(步驟S13)。於升溫處理中，於羧酸氣體之氧化膜之還原溫度T1以上且未達焊料凸塊22之熔點T2之溫度區域，降低羧酸氣體之濃度。即，利用氣體流量控制器157、158進行控制，增加稀釋氣體配管162內流動之惰性氣體相對於混合氣體之流量比率。藉此，可降低加熱爐110內之羧酸氣體濃度。如上所述，並非將加熱爐110內之羧酸氣體濃度變成0，而是降低至特定值C2。特定值C2係於升溫工序結束時間點(下一熔融工序開始時間點)能夠將焊料凸塊22與凸塊電極11、23之間咬入之氧化膜32還原之最低限度的羧酸氣體濃度。再者，以加熱爐110之環境氣壓固定、例如成為2.7×104 Pa之狀態之方式控制排氣閥17。
於使用甲酸作為羧酸之情形時，例如以15L/分之比率，流通例如以還原溫度T1以上時甲酸氣體濃度為2.8體積%之方式控制含有甲酸氣體之混合氣體與稀釋氣體之流量比之還原性氣體。然後，當加熱爐110之溫度達到焊料凸塊22之熔點T2時，例如以30L/分之比率，流通以甲酸氣體濃度為0.6體積%以上之方式控制含有甲酸氣體之混合氣體與稀釋氣體之流量比之還原性氣體。再者，甲酸氣體濃度為一例，還原溫度T1以上時理想的是2.8體積%～9.2體積%，且當達到焊料凸塊22之熔點T2時理想的是0.6體積%～2.8體積%。藉此，階段性地降低加熱爐110內之甲酸氣體濃度。該設定中，甲酸氣體濃度以-0.7體積%/分減少。但，以加熱爐110內之整體壓力不變化的方式控制。
然後，將加熱爐110之溫度維持為焊料凸塊22之熔點T2以上，實施熔融焊料凸塊22之熔融處理(步驟S14)。於熔融處理之開始時間點，如上所述，加熱爐110內為能將焊料凸塊22與凸塊電極11、23之間咬入之氧化膜32還原之最低限度的羧酸氣體濃度。於熔融處理期間，加熱爐110內之整體壓力亦控制為不變化。
根據相對於溫度繪製氧化反應之標準反應吉布斯能比之埃林厄姆圖，例如使用Sn、Ag、Cu、Au、Bi、Zn、In等或其複合膜、合金等之焊料凸塊22係以不易被還原之Sn為主成分之金屬。但，依據該方法，藉由使用於還原溫度T1以上具有還原作用之羧酸氣體，而於未達焊料凸塊22之熔點T2之低溫區域除去氧化膜。另一方面，例如使用Cu、Au、Ni、Pd等單體、複合膜、合金等之凸塊電極11、21、23於高溫下容易被還原。因此，藉由還原處理將焊料凸塊22之表面之氧化膜32大致除去後，以降低加熱爐110內之羧酸氣體濃度之狀態，設為焊料凸塊22之熔點T2，從而可抑制凸塊電極11、21、23之氧化膜31之還原。
又，根據作為積層體50暫時固定之圖2(b)之狀態，未達熔點T2時可能出現羧酸氣體滲入凸塊電極11與焊料凸塊22之接觸界面27之間隙G之狀態之情形。總之，變成焊料凸塊22變形而覆蓋凸塊電極11、23之狀態。焊料凸塊22於熔點T2以上熔融而焊料形狀變化，羧酸氣體能夠滲入，因此可繼續除去焊料凸塊22之氧化膜32。所以，加熱爐110內至少於熔融處理之開始時間點為暫時具有還原性之狀態。即，加熱爐110內之溫度達到熔點T2時之羧酸氣體之濃度被控制為具有能夠除去凸塊電極11、23與焊料凸塊22之間之氧化膜32之最低限度的濃度，且小於還原溫度T1下之羧酸氣體之濃度。
再者，於熔融處理之結束時間點，可具有能夠除去氧化膜32之最低限度的羧酸氣體之濃度，亦可具有未達最低限度的羧酸氣體之濃度。於使用甲酸作為羧酸之情形時，例如達到熔點T2時之羧酸氣體濃度只要為0.6體積%以上即可。
藉由於此種加熱爐110內之氣氛下將溫度設為熔點T2以上，凸塊電極11、23與焊料凸塊22一體化而形成接合體25。此時，於殘留凸塊電極11、23之氧化膜31之狀態下熔融焊料凸塊22，因此熔融之焊料不會向凸塊電極11、23之側面潤濕擴散，形成能比穩定之焊料凸塊22之連接形狀。焊料凸塊22之穩定之連接形狀例如為球形狀。其結果，如圖2(c)所示，可獲得由實現電及機械特性優異之半導體晶片10、20間之連接之積層體50形成之半導體裝置。
然後，實施排氣處理(步驟S15)。於排氣處理中，停止載物台111之加熱機構之加熱，且停止還原性氣體向加熱爐110內之供給，利用真空泵132將加熱爐110內排氣。
使加熱爐110內之溫度降溫至容易取出積層體50之溫度、例如50℃左右之溫度後，實施大氣開放處理(步驟S16)。於大氣開放處理中，經由配管151自惰性氣體貯存部152向加熱爐110內導入氮氣等惰性氣體而使其變成大氣壓。然後，自加熱爐110中取出配置有複數個積層體50之搬送板60。這樣，加熱爐110內恢復成大氣壓，可於降溫至容易取出積層體50之溫度後實施，亦可於還原處理結束後，於加熱爐110內之溫度處於焊料凸塊22之熔點T2以上之溫度區域之狀態下，向加熱爐110內一次性導入氮氣等惰性氣體而恢復成大氣壓。
將自加熱爐110取出之積層體50與通常之半導體裝置同樣地送往裝配工序。裝配工序根據半導體裝置而選擇，並無特別限定。若敍述其一例，例如於未圖示之配線基板上利用熱硬化性樹脂黏結積層體50，將其固化處理而硬化後，利用引線接合等將積層體50與未圖示之基板之間連接。將此種結構體樹脂模塑後，配置外球而形成半導體裝置(半導體封裝)之外部連接端子。
於第1實施形態中，於對暫時固定有半導體晶片10、20之凸塊電極11、23、與另一半導體晶片20之焊料凸塊22之積層體50進行還原回焊處理時，以羧酸氣體之還原溫度T1以上且未達焊料凸塊22之熔點T2之溫度向加熱爐110內導入羧酸氣體。然後，於加熱爐110內之溫度達到焊料凸塊22之T2之時間點，變成能夠將夾於焊料凸塊22與凸塊電極11、23之間之焊料凸塊22之氧化膜32還原之最低限度的羧酸氣體之濃度。藉此，於焊料凸塊22熔融時，一面抑制凸塊電極11、23之側面存在之氧化膜31之還原，一面進行焊料凸塊22上殘留之氧化膜32之還原。其結果，凸塊電極11、23與凸塊電極21之間連接所需之焊料體積不會減少，可形成具有穩定連接形狀之焊料凸塊22。又，可對連接面之焊料充分賦予合金層生長所需之加熱時間，從而可增加焊料凸塊22之連接強度。
(第2實施形態)圖6係表示第2實施形態之還原回焊處理之條件之一例之圖。該圖中橫軸表示時間，左側之縱軸表示溫度，右側之縱軸表示加熱爐110內之甲酸之濃度(體積%)。再者，以下僅說明與第1實施形態之圖5不同之部分。
第2實施形態中，將圖5之步驟S12之還原處理與步驟S13之升溫處理組合而變成1個還原處理(步驟S21)。該還原處理中，以於羧酸氣體之還原溫度T1以上且未達焊料凸塊22之熔點T2之溫度，使羧酸氣體濃度階段狀降低之方式變更還原性氣體濃度。例如，如圖6所示，於時刻T11～T12，以羧酸氣體濃度變成C1之方式導入第1還原性氣體，於時刻T12～T13以羧酸氣體濃度變成C3之方式導入第2還原性氣體，於時刻T13～T14以羧酸氣體濃度變成C2之方式導入第3還原性氣體。其中，羧酸氣體濃度之大小為C1＞C3＞C2。濃度不同之還原性氣體導入之切換時間、及導入之還原性氣體之羧酸氣體濃度之設定可根據凸塊電極11、23及焊料凸塊22之形態而任意地設定，其次數及濃度並無限制。即，當加熱爐110內之溫度達到熔點T2時，只要以羧酸氣體濃度具有能夠將夾於焊料凸塊22與凸塊電極11、23之間之焊料凸塊22之氧化膜32還原之最低限度的羧酸氣體之濃度之方式，使羧酸氣體濃度以m(m為2以上之自然數)階段狀降低即可。
根據第2實施形態，亦能獲得與第1實施形態相同之效果。
再者，上述說明中，如圖1及圖2所示，表示了於其中一半導體晶片20之凸塊電極21上配置焊料凸塊22之情形，但亦可於兩個半導體晶片10、20之凸塊電極11、21、23上配置焊料凸塊22。又，對於具備凸塊電極11、21、23之玻璃環氧基板與配置有焊料凸塊22之半導體晶片20、或者具備焊料凸塊22之玻璃環氧基板與半導體晶片之凸塊電極11、21、23之接合亦係一樣之。該等情形時，亦藉由相同之方法進行還原回焊處理，可形成利用2個焊料凸塊22具有穩定連接形狀之接合體。
雖然對本發明之若干實施形態進行了說明，但該等實施形態係作為示例而提出者，並不意圖限定發明之範圍。該等新穎之實施形態能以其他各種形態實施，且於不脫離發明主旨之範圍內可進行各種省略、置換、變更。該等實施形態及其變化包含於發明之範圍及主旨，且包含於申請專利範圍記載之發明及其均等範圍內。 相關申請引用 本申請以2019年3月15日先行申請之日本專利申請第2019-048423號之優先權之利益為基礎，且要求其利益，藉由引用之方式包含該申請之全部內容。
10:半導體晶片 11:凸塊電極 17:排氣閥 20:半導體晶片 20-1:半導體晶片 20-2:半導體晶片 20-N:半導體晶片 21:凸塊電極 21a:焊料 22:焊料凸塊 23:凸塊電極 25:接合體 27:接觸界面 31:氧化膜 32:氧化膜 40:支持基板 50:積層體 60:搬送板 100:還原回焊處理裝置 110:加熱爐 111:載物台 130:排氣處理部 131:配管 132:真空泵 133:排氣閥 134:除外裝置 150:氣體導入部 151:配管 152:惰性氣體貯存部 153:閥 155:惰性氣體貯存部 156:還原氣體生成部 157:氣體流量控制器 158:氣體流量控制器 161:配管 162:稀釋氣體配管 163:載氣配管 164:混合氣體配管 165:閥 1561:密閉容器 1562:羧酸液體 1563:加熱部 C:羧酸氣體濃度 P:壓力 T:溫度 T1:還原溫度 T2:熔點
圖1(a)～(c)係模式性表示第1實施形態之半導體裝置之製造方法之順序之一例的剖視圖。  圖2(a)～(c)係模式性表示第1實施形態之半導體裝置之製造方法中之焊料凸塊附近之狀況的剖視圖。  圖3係模式性表示焊料凸塊連接時之狀況之圖。  圖4係模式性表示還原回焊處理裝置之構成之一例之圖。  圖5係表示第1實施形態之還原回焊處理之條件之一例之圖。  圖6係表示第2實施形態之還原回焊處理之條件之一例之圖。
C:羧酸氣體濃度
P:壓力
T:溫度
T1:還原溫度
T2:熔點

Claims (11)

  1. 一種半導體裝置之製造方法，其包括：積層體形成工序，其係將具有第1凸塊電極及配置於上述第1凸塊電極上之焊料凸塊之第1半導體元件、與具有第2凸塊電極之第2半導體元件，藉由暫時固定上述焊料凸塊與上述第2凸塊電極而積層，從而形成積層體；排氣工序，其係將配置有上述積層體之爐內排氣；氧化膜除去工序，其係一面將上述爐內之溫度設為顯現羧酸之還原作用之還原溫度以上、且未達上述焊料凸塊熔融之熔融溫度之溫度，一面以上述爐內變成第1羧酸氣體濃度之方式，向上述爐內導入包含羧酸氣體與惰性氣體之還原性氣體，來將上述焊料凸塊之表面之氧化膜除去；還原性氣體濃度降低工序，其係一面將上述爐內之溫度升溫至上述熔融溫度為止，一面將上述爐內之羧酸氣體之濃度降低至第2羧酸氣體濃度為止；及熔融工序，其係將上述爐內之溫度維持為上述熔融溫度以上之溫度，使上述焊料凸塊熔融，從而將上述焊料凸塊與上述第2凸塊電極連接；且上述第2羧酸氣體濃度係低於上述第1羧酸氣體濃度，且係包含能使咬入上述焊料凸塊與上述第2凸塊電極之間之上述焊料凸塊之氧化膜還原之最低限度的羧酸氣體之濃度，於上述熔融工序之開始時間點，至少上述爐內具有上述第2羧酸氣體濃度。
  2. 一種半導體裝置之製造方法，其包括：積層體形成工序，其係將具有第1凸塊電極及配置於上述第1凸塊電極上之焊料凸塊之第1半導體元件、與具有第2凸塊電極之第2半導體元件，藉由暫時固定上述焊料凸塊與上述第2凸塊電極而積層，從而形成積層體；排氣工序，其係將配置有上述積層體之爐內排氣；氧化膜除去工序，其係一面將上述爐內之溫度升溫至上述焊料凸塊熔融之熔融溫度為止，一面向上述爐內導入羧酸氣體與惰性氣體，從而將上述焊料凸塊之表面之氧化膜除去；熔融工序，其係將上述爐內之溫度維持為上述熔融溫度以上之溫度，使上述焊料凸塊熔融，而將上述焊料凸塊與上述第2凸塊電極連接；及第2排氣工序，其係降低上述爐內之溫度，並將上述爐內排氣；且於上述氧化膜除去工序中，於上述排氣工序之後，向上述爐內以變成第1羧酸氣體濃度之方式導入上述羧酸氣體與上述惰性氣體後，於上述熔融工序之開始時間點，以變成低於上述第1羧酸氣體濃度之第2羧酸氣體濃度之方式，階段性地降低上述羧酸氣體之濃度，以此方式控制上述羧酸氣體與上述惰性氣體之導入量，上述第2羧酸氣體濃度係低於上述第1羧酸氣體濃度，且係包含能夠將咬入上述焊料凸塊與上述第2凸塊電極之間之上述焊料凸塊之氧化膜還原之最低限度的羧酸氣體之濃度。
  3. 如請求項1或2半導體裝置之製造方法，其中至上述熔融工序結束為止，將上述爐內維持為上述第2羧酸氣體濃度。
  4. 如請求項1或2之半導體裝置之製造方法，其中於上述熔融工序之結束時間點，上述爐內未達上述第2羧酸氣體濃度。
  5. 如請求項1之半導體裝置之製造方法，其中於上述氧化膜除去工序至上述熔融工序期間，將上述爐內之壓力維持在較大氣壓低之特定壓力。
  6. 如請求項5之半導體裝置之製造方法，其中上述壓力為1.3×104 Pa以上8×104 Pa以下之範圍。
  7. 如請求項1之半導體裝置之製造方法，其中上述第1羧酸氣體濃度為大於0.6體積%且9.2體積%以下。
  8. 如請求項7之半導體裝置之製造方法，其中上述第1羧酸氣體濃度為2.8～9.2體積%，上述第2羧酸氣體濃度為0.6～2.8體積%。
  9. 如請求項1之半導體裝置之製造方法，其中上述第1凸塊電極及上述第2凸塊電極，包含選自Ni、Cu、Au及Pd之群之1種金屬、或選自Ni、Cu、Au及Pd之群之2種以上之金屬積層多層而成之複合膜，上述焊料凸塊由Sn或包含Sn之合金形成。
  10. 如請求項1之半導體裝置之製造方法，其中上述羧酸氣體中包含之羧酸為脂肪族一元或二元之低級羧酸。
  11. 如請求項10之半導體裝置之製造方法，其中上述低級羧酸包含選自甲酸、乙酸、丙烯酸、丙酸、草酸、琥珀酸及丙二酸之群之至少1種。
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