本研究主要在探討使用氮化鉭薄膜作為擴散阻障層材料，並應用於銅連接導線製程中，與低介電常數絕緣層間之熱反應性質研究。所使用的氮化鉭薄膜分別是初鍍時為非晶質相的TaNx~0.5及Ta : N元素成1:1計量比之多晶結構TaN薄膜，而所使用的低介電常數材料則包括含氟二氧化矽(FSG)及含碳二氧化矽(OSG)。吾人首先觀察並比較銅/氮化鉭/介電薄膜(Cu/Ta-N/Ta/dielectric layer)結構在經過不同溫度的真空退火處理前後之性質變化，利用四點探針量測各試片在退火處理前後的片電阻值，並以θ-2θ X光繞射儀、低掠角X光繞射儀、掃描式電子顯微鏡及穿透式電子顯微鏡觀察試片的微結構變化，同時，也利用歐傑能譜分析儀、拉賽福背向散射分析儀及二次離子質譜儀分析試片中各元素的縱深分佈狀況，以評估銅原子的擴散行為、氮化鉭薄膜的阻障能力及低介電常數薄膜的熱穩定性。而後，再對低介電常數薄膜進行性質分析，用以闡明介電薄膜的特性對多層結構試片進行退火處理後的性質之影響，包括以熱脫附常壓質譜儀量測介電薄膜的釋氣現象，以X光光電子能譜儀及傅立葉轉換紅外線光譜儀分析薄膜的鍵結型態，最後，針對介電薄膜進行電性分析，量測經過不同方法進行前處理之介電薄膜之電容-電壓(C-V)曲線及漏電流密度-電場(J-E)曲線，以瞭解介電薄膜的介電常數及漏電流密度變化趨勢。
實驗結果顯示，初鍍為非晶質相的TaNx~0.5薄膜，在真空退火處理溫度達到800 oC時，仍能表現出較TaN為佳的抗銅及氟元素擴散的能力。然而在更高的退火處理溫度時，由於TaNx~0.5晶粒急劇成長所引起的拉伸應力將造成TaNx~0.5薄膜出現破孔，引起試片的嚴重劣化。若將Cu/Ta-N/Ta多層薄膜鍍製於未經任何前處理的FSG介電層之上，在經過400 oC的真空退火處理後，試片表面會出現許多氣泡狀的突起，以OSG作為介電層材料時則無此現象。此和FSG所吸附大量的水氣釋放時所引起的應力有關。
經由Cu/Ta-N/Ta/FSG(OSG)/<Si>試片退火處理前後的截面觀察分析，可發現在退火處理之後，Ta/FSG界面處附著性不佳，甚且會有氣泡狀的空孔出現在Ta薄膜的下方，此乃是由於FSG薄膜受熱之後的釋氣現象所造成。經由XPS對此Ta/FSG界面進行分析，則可觀察到Ta-F化合物的生成，這也是造成界面附著強度降低的原因之ㄧ。
FSG及OSG薄膜在氮氣氛保護下進行400 oC、30分鐘的預先熱處理後的性質分析結果顯示，此預先熱處理步驟對這兩種低介電常數薄膜皆有穩定化的效果，FSG薄膜尤其明顯。兩者在預先熱處理過程中皆能夠將所吸附的水氣有效地釋放出，FSG薄膜中一些較不穩定的Si-F鍵結也能夠經由此一程序去除，避免了在後續熱處理步驟時釋出的氟可能和上層鉭金屬層產生的反應。FSG在真空退火處理60分鐘之後，其介電常數值會低於初鍍時之量測值，經由光學模擬分析的結果可知，FSG薄膜在熱處理之後密度變低，可能是由於氟元素的釋出及結構上的變化導致。此外，雖然一般咸認為OSG薄膜的機械性質不佳，然而其熱脫附分析的結果顯示OSG薄膜的熱穩定性極為優良，在升溫達到400 oC以上時，才會有極微量的CH3+脫附訊號被偵測出。
本研究的結果顯示，初鍍非晶質相的TaNx~0.5薄膜具有較良好的銅擴散阻障性質。然而當其運用在未經前處理之FSG介電薄膜上時，將會因為和介電層中所釋出的氟及水氣反應，造成劣化的效應，使其阻障效果及結構完整性大幅減低。而TaNx~0.5配合經過預先熱處理的FSG或是OSG薄膜時則無附著性或是結構劣化的問題。因此，為了獲得較佳的元件可靠度及效能，在鍍製金屬薄膜於FSG介電層之前對介電材料進行預先熱處理為一重要的步驟。

In this study, the characteristics of various Cu/Ta-N/dielectric /<Si> structures before and after heat treatment were explored. Dielectric materials with low dielectric constants used in this study were fluorinated silicate glass (FSG) and organosilicate glass (OSG). The FSG and OSG films were deposited onto silicon wafers in a single-wafer CVD chamber. Ta, Ta-N and Cu layers were then deposited sequentially on the dielectric layers by magnetron sputtering. The Ta-N films prepared with 1% and 5% of nitrogen flow ratio (N2/(N2+Ar)) are amorphous TaNx~0.5 and polycrystalline TaN, respectively. After deposition, all the specimens were annealed in vacuum at various temperatures for 60 min to investigate their thermal interactions.
The experimental results indicate that the ability of the amorphous TaNx~0.5 film, to prevent copper and fluorine from diffusing, is superior to that of the polycrystalline TaN upon annealing at 800 oC in vacuum. However, TaNx~0.5 film degrades seriously after annealing at 900 oC. It is caused by the tensile stress produced as the Ta2N grains grow. On the other hand, bubble-like topography was observed on the surfaces of the Cu/Ta-N/Ta multilayers deposited on FSG but not seen for the multilayers deposited on OSG. It should be attributed to the significant stress produced by the release of moisture from the FSG film.
The cross-sectional TEM bright-field micrographs of the Cu/TaNx~0.5/Ta/FSG/ <Si> show that voids were formed at the interface between TaNx~0.5/Ta bi-layer and FSG film after post metallization annealing. It is caused by the evolution of moisture from the FSG film. The formation of tantalum fluoride, lowering the adhesion strength of the Ta/FSG interfaces, can be observed by using X-ray photoelectron spectroscopy. The experimental results show that both of FSG and OSG are “stabilized” by pre-baking treatment (400 oC/30 min, in N2) before metallization. It means that the unstable Si-F bonds in the FSG film can be eliminated by thermal treatment.
It is noticed that the dielectric constant of FSG film will decrease after annealing at 400 oC in vacuum for 60 min. By comparing the k values of as-prepared FSG with/without water-soaking treatment, it is clear that the main factor altering the k values of FSG is the moisture content. Pre-baking (400 oC in N2 ambient for 30 min) treatment is effective to drive the moisture out of the dielectrics and the water-soaking process brings the moisture back. Nevertheless, the 400 oC/60 min annealing further reduces the k values to be even lower than that of as-deposited FSG. It may be due to the loss of fluorine and/or the instability of the FSG structure. Therefore, the further reduction in the dielectric constant of the 400 oC/60 min-annealed FSG films is attributed to the decrease in the film density of the FSG dielectric layers upon annealing. On the other hand, the OSG possesses better water resistance and thermal stability. The functional groups incorporated in the OSG film will not be released upon annealing to 400 oC.
In summary, this study investigates the influences of the moisture and unstable fluorine in the FSG dielectric layer on the integrity of the Cu/Ta-N/Ta/FSG/<Si> multilayer structure. In comparison, the specimens with the Cu/Ta-N/Ta/OSG/<Si> structure were also investigated. The results indicate that the moisture absorbed in the FSG film increases the dielectric constant drastically. Furthermore, leakage current density of the FSG dielectric layer is affected by the moisture content in the dielectric layer, too. This study shows that the outgassing from dielectrics might deteriorate the performance of the IC devices. Therefore, baking the FSG dielectric adequately prior to the subsequent metallization is essential.

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