Copper Electroplating Composition With Polyaminoamide Leveling
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Solution Overview
Problem
Existing copper electroplating technologies face challenges in achieving uniform deposition on substrates with small features, often resulting in defects like voids and mounding, particularly in nanometer and micrometer-scale features, and require extensive post-deposition processing.
Innovation Solution
The use of polyaminoamides, alkoxylated polyaminoamides, functionalized polyaminoamides, and functionalized alkoxylated polyaminoamides as additives in copper electroplating baths, which provide improved leveling properties, reducing overplating and defect formation, and enabling more efficient copper layer deposition on substrates with varying aperture sizes.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Manufacturing precision
If conventional additives are used in copper electroplating baths, then copper deposition can occur, but uniform deposition on small features is not achieved, resulting in defects like voids and mounding
Solution Approach 1:
The patent changes the chemical parameters of the electroplating bath by introducing polyaminoamides with specific molecular structures (formula I) containing amino groups that can interact with copper ions. This chemical parameter change enables uniform deposition on small features by modifying the deposition mechanism at the molecular level, preventing both voids and mounding defects
Solution Approach 2:
The patent uses composite additive systems combining polyaminoamides with other electroplating chemicals. The polyaminoamide component (formula I) works synergistically with other bath additives to achieve uniform copper deposition on small features while preventing defects, creating a composite chemical environment that solves the deposition uniformity problem
2Manufacturing precision
If extensive copper deposition is performed to fill features, then feature filling is achieved, but overplating and mounding occur requiring extensive post-deposition processing
Solution Approach 1:
The polyaminoamide additive performs preliminary action by adsorbing onto feature surfaces before copper deposition begins, creating a controlled interface that directs copper growth. This preliminary surface modification ensures uniform deposition and complete feature filling without excessive copper accumulation, eliminating the need for extensive post-deposition removal
Solution Approach 2:
The polyaminoamide acts as a feedback mechanism by continuously adsorbing and desorbing during deposition, sensing local copper concentration and deposition rate. This dynamic feedback controls copper ion reduction at the cathode surface, maintaining uniform deposition rates that fill features completely without creating mounding that would require removal
3Manufacturing precision
If copper electroplating is performed on substrates with nanometer and micrometer scale features, then feature filling is attempted, but defects like voids form within the features
Solution Approach 1:
The polyaminoamide additive provides local quality control by preferentially adsorbing at specific locations (feature openings and sidewalls) with different local conditions. This localized adsorption creates different deposition rates at different locations, ensuring uniform copper growth throughout the feature volume and preventing void formation in the center of nanometer and micrometer scale features
Applied Scientific Principles
This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.
Function Achieved in This Case
The described additives result in substantially planar copper layers with reduced voids and mounding, requiring less material removal during post-deposition processes, such as CMP, and enhance the filling of features like through-silicon vias and microvia plating, leading to reduced operational time and defect risk.
Implementation Method 1
levelers are used to provide a substantially planar surface over the filled features... polyaminoamides... can be used as additives, in particular leveling agents, in copper electroplating baths
Implementation Method 2
Filling of small features, such as vias and trenches, by copper electroplating is an essential part of the semiconductor manufacture process
Implementation Method 3
copper electroplating baths... applying a current to the substrate to deposit a copper layer onto the substrate
Data Source
AI summary
A composition comprising a source of copper ions and at least one additive comprising at least one polyaminoamide represented by formula I or derivatives of a polyaminoamide of formula I obtainable by complete or partial protonation or acylation, wherein D1 is, for each repeating unit 1 to p independently, selected from a chemical bond or a divalent group selected from C1-C20-alkanediyl group which may optionally be interrupted by a double bond and/or an imino group and/or is optionally, completely or partially, a constituent of one or more saturated or unsaturated carbocyclic 5- to 8-membered rings; D2, D3 are independently selected from straight chain or branched C1 to C6 alkanediyl; R1 is, for each repeating unit 1 to n independently, selected from -(CR11R12-CR13R14-O)q-H; R11, R12, R13, R14 are each independently selected from hydrogen, C1-C10-alkyl, CH2-O-alkyl; E1, E2 are independently selected from (a) a nucleophilically displaceable leaving group X, (b) NH-C1-C20-alkyl or NH-C1-C20-alkenyl, (c) H-{NH-[02-NR1]n-D3-NH} or R2-{NR2-[D2-NR1]n-D3-NH}, (d) C1-C20-alkyl-CO-{NH-[D2-NR2]n-D3-NH}, and (e) C1-C20-alkenyl-CO-{N H-[D2-NR2]n-D3-NH}; n is an integer from 1 to 250; p is an integer from 2 to 150; q is the number of alkoxy groups CR11R12-CR13R14-O averaged over the polymer units 1 to n and is from 0.1 to 5.