Tuning Charge Order in (TMTTF)<sub>2</sub><i>X</i> by Partial Anion Substitution

oleh: Andrej Pustogow, Daniel Dizdarevic, Sebastian Erfort, Olga Iakutkina, Valentino Merkl, Gabriele Untereiner, Martin Dressel

Format: Article
Diterbitkan: MDPI AG 2021-12-01

Deskripsi

In the quasi-one-dimensional (TMTTF)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula><i>X</i> compounds with effectively quarter-filled bands, electronic charge order is stabilized from the delicate interplay of Coulomb repulsion and electronic bandwidth. The correlation strength is commonly tuned by physical pressure or chemical substitution with stoichiometric ratios of anions and cations. Here, we investigate the charge-ordered state through partial substitution of the anions in (TMTTF)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>[AsF<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>6</mn></msub></semantics></math></inline-formula>]<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mrow><mn>1</mn><mo>−</mo><mi>x</mi></mrow></msub></semantics></math></inline-formula>[SbF<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>6</mn></msub></semantics></math></inline-formula>]<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>x</mi></msub></semantics></math></inline-formula> with <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi>x</mi><mo>≈</mo><mn>0.3</mn></mrow></semantics></math></inline-formula>, determined from the intensity of infrared vibrations, which is sufficient to suppress the spin-Peierls state. Our dc transport experiments reveal a transition temperature <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>T</mi><mi>CO</mi></msub></semantics></math></inline-formula> = 120 K and charge gap <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mo>Δ</mo><mi>CO</mi></msub></semantics></math></inline-formula><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>=</mo><mn>430</mn></mrow></semantics></math></inline-formula> K between the values of the two parent compounds (TMTTF)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>AsF<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>6</mn></msub></semantics></math></inline-formula> and (TMTTF)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>SbF<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>6</mn></msub></semantics></math></inline-formula>. Upon plotting the two parameters for different (TMTTF)<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula><i>X</i>, we find a universal relationship between <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>T</mi><mi>CO</mi></msub></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mo>Δ</mo><mi>CO</mi></msub></semantics></math></inline-formula> yielding that the energy gap vanishes for transition temperatures <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>T</mi><mi>CO</mi></msub></semantics></math></inline-formula><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>≤</mo><mn>60</mn></mrow></semantics></math></inline-formula> K. While these quantities indicate that the macroscopic correlation strength is continuously tuned, our vibrational spectroscopy results probing the local charge disproportionation suggest that <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mn>2</mn><mi>δ</mi></mrow></semantics></math></inline-formula> is modulated on a microscopic level.