Method of electroplating copper into a via on a substrate from an acid copper electroplating bath

A technology of copper electronics and substrates, which is applied to circuits, electrical components, semiconductor devices, etc., and can solve problems such as surface defects of unresolved copper deposits

Active Publication Date: 2017-05-03
ROHM & HAAS ELECTRONICS MATERIALS LLC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this patent does not address the problem of surface defects in such copper deposits

Method used

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  • Method of electroplating copper into a via on a substrate from an acid copper electroplating bath
  • Method of electroplating copper into a via on a substrate from an acid copper electroplating bath
  • Method of electroplating copper into a via on a substrate from an acid copper electroplating bath

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0067] by first combining 60g / L from CuSO 4 ·5H 2 O Cu 2+ 、60g / L H 2 SO 4 and 50 mg / L of Cl from 1N HCl - , followed by the addition of 6 mg / L accelerator bis(sulfopropyl) sodium disulfide from the stock solution, 17.5 mg / L leveler which is the reaction product of butyl diglycidyl ether, 75% 4-phenylimidazole, and 25% imidazole from the stock solution to prepare the copper electroplating bath. Each bath included Inhibitors 1 and 2 in the amounts shown in Table 1 below.

[0068] Table 1

[0069]

[0070]

[0071] R is a branched 2-ethylhexane moiety. The HLB of the triblock copolymer was determined to be 19 using the Davis method. The following table lists the variables used to calculate the HLB by the Davis method:

[0072] Table 2

[0073] EO% lm w Mw PO #EO group #PO group #CH group # ether base #OH group 40 1680 2520 38 43 205 81 2

example 2

[0075]Via fill tests were performed on a number of test wafer coupons with TSVs of 5 μm diameter x 55 μm depth. The coupons were connected to the plating head of the segmented plater with conductive copper tape, which was then covered with plater tape (3M, Minneapolis, MN). All coupons were sprayed with deionized water for 5 minutes prior to plating. Each wafer coupon was used as a cathode and was spun by an in-house instrument MSRX rotator at 50 rpm and contacted with the plating bath from Example 1. The temperature of the electroplating bath was 25°C. The plating waveforms used to monitor surface (eddy current) defects are reported in Table 3, where CD is the current density. The dynamic surface tension of each plating bath was measured at 25°C using a Cruise BP100 bubble pressure tensiometer at a surface age of 30 seconds and found to be 36.7 mN / m.

[0076] table 3

[0077]

[0078] After copper plating to fill the TSVs, the wafer coupons were cross-sectioned and ima...

example 3

[0080] The method disclosed in Example 2 was repeated, but the inhibitor combination had the components in Table 4.

[0081] Table 4

[0082]

[0083] R is as defined in Example 1 above. The HLB of the triblock copolymer was determined to be 24 using the Davis method. The following table lists the variables used to calculate the HLB:

[0084] table 5

[0085] EO% lm w Mw PO #EO group #PO group #CH group # ether base #OH group 50 2300 2300 52 40 224 92 2

[0086] After filling the TSVs, they were analyzed by the same method as described in Example 2. No voids were observed in the sample. The cross-section of the sample looks similar to figure 1 Basically the same as shown in . All samples had a bright copper surface. There were no observable defects on the copper deposit.

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Abstract

Copper electroplating baths containing primary alcohol alkoxylate block copolymers and ethylene oxide / propylene oxide random copolymers having specific HLB ranges are suitable for filling vias with copper, where such copper deposits are substantially void-free and substantially free of surface defects.

Description

technical field [0001] The present invention is directed to a method of electroplating copper from an acidic copper electroplating bath into through-holes on a substrate. More specifically, the present invention is directed to a method of electroplating copper from an acidic copper electroplating bath into vias on a substrate, wherein the copper deposit has a substantially void-free via fill and a defect-free surface. Background technique [0002] Copper is widely used in the manufacture of electronic devices, including integrated circuit (IC) devices. For example, the copper damascene process used to manufacture integrated circuits involves forming a damascene copper wiring pattern while forming via connections between metal layers. In such processes, copper is deposited electrolytically. A variety of copper electroplating formulations have been developed to meet the unique needs of depositing copper for extremely small sized features (eg < 150 nm) used in damascene me...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25D3/38C25D7/12C25D5/02H01L21/288H01L21/768
CPCC25D3/38C25D5/02C25D7/123H01L21/2885H01L21/76898H01L21/76873H01L21/76879
Inventor M·托尔塞斯M·斯卡利西C·西罗
Owner ROHM & HAAS ELECTRONICS MATERIALS LLC
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