@Luke Harold Miles the purpose of the circuit is NOT to have DIFFOUT_N and OUT to a known value during calibration, but to have the OUT signal to either logic 1 or logic 0, correctly detecting 1mV differential input. Such small input signals can be reliably detected only with a self calibration. With zero differential input you ensure the differential and gain stages are at the trip point. This happens when START=0. Then you apply the differential input and set START to 1, this initiates the sensing step.
Below image shows 100 runs with device mismatch enabled, plus variations on VCC and temperature as shown in the graphs. At the end of the sensing operations (look at the cursor positions) you have the correct output amplifying the 1mV input differential signal. The value of OUT before sensing is not of any interest.
The calibration step is done before any sensing operations. This is necessary for 2 reasons.
• the calibration value of the ADJ pin is stored on a capacitor that will eventually discharge over time.
• Repeating calibration before any measure will track variations in temperature / vcc / anything else.