Table 1 Reactivity, TE performance and film thickness of PEDOT polymerized via different precursors

	Precursor composition and film thickness							Reactivity and TE performance (298 K)
Method	Anion	pKa ^a	Ox (wt%)	Py (wt%)	PEPG (wt%)	Extra acid (wt%)	Max. thickness (nm)	t (s)	σ (S cm⁻¹)	S (μV K⁻¹)	S²σ (μW mK⁻²)	Sample no. /ref.
CP	OTs	−2.8³⁹	20.0	0	0	0	80	0.5	19.3	13.2	0.336	P1-a
			19.7	1. 4↓	0	0	200	—	~300	~40	38	ref. 29
	CSA	1.2³⁹ (1.17^b)	66.7^c	0	0	5. 0↑	700	25	752	26.4	52.4	P2
			70.2^c	0	0	0	—	∞	—	—	—	—
VPP	OTs	−2.8³⁹	40.0^d	0	0	0	420	18	21	35.3	2.61	P1-b
			33.3^d	0	16.7↓	0	280	300	589	22.4	29.6	P1-c
			33.0^d	1. 1↓	16. 5↓	0	250	840	812	24.3	47.9	P1-d
			20.0	1.0↓	20.0↓	0	120	—	1550	14.9	34.4	ref. 28
	DBSA	−1.84^40,41 (−0.45^b)	78.1^e	0	0	0	1790	1500	1140	24.7	69.6	P4
	BNSA	0.37^b	68.6^d	0	0	5.0↓	820	2100	200	26.7	14.3	P3
			72.2^d	0	0	0	—	∞	—	—	—	—

Abbreviations: BNSA, butylnaphthalenesulfonate; CSA, camphorsulfonate; CP, casting polymerization; DBSA, dodecylbenzenesulfonate; OT, tosylate; Ox, oxidant; PEDOT, poly(3,4-ethylenedioxythiophene); PEPG, poly(ethylene glycol); Py, pyridine; TE, thermoelectric; VPP, vapor phase polymerization.
The maximum film thickness (±5 nm) and approximate reaction completion time (t, ±20%) are affected by the precursor composition including Ox, base inhibitor (Py), copolymer inhibitor (PEPG) and extra acid. Down arrow: inhibitors used to decrease the reaction rate. Up arrow: extra acid used to accelerate the reaction. ∞: non-reactive.
Aqueous pKa value of corresponding acid.
^bCalculated result by ACD Lab.⁴²
^cMaximum oxidant concentration at 25 °C. Too viscous to mix with monomer at higher concentration.
^dMaximum oxidant concentration at 25 °C. Limited solubility.
^eMaximum oxidant concentration at 25 °C. Too viscous for spin-coating at higher concentration.

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